CN102666620A - Hydrophilically-modified silicone compositions - Google Patents
Hydrophilically-modified silicone compositions Download PDFInfo
- Publication number
- CN102666620A CN102666620A CN2010800586639A CN201080058663A CN102666620A CN 102666620 A CN102666620 A CN 102666620A CN 2010800586639 A CN2010800586639 A CN 2010800586639A CN 201080058663 A CN201080058663 A CN 201080058663A CN 102666620 A CN102666620 A CN 102666620A
- Authority
- CN
- China
- Prior art keywords
- component
- ester
- acid
- silicone
- extract
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 155
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 claims abstract description 55
- -1 siloxanes Chemical class 0.000 claims description 246
- 239000000284 extract Substances 0.000 claims description 116
- 239000012530 fluid Substances 0.000 claims description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 150000001875 compounds Chemical class 0.000 claims description 62
- 150000002148 esters Chemical class 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000000839 emulsion Substances 0.000 claims description 40
- 230000036541 health Effects 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 238000010521 absorption reaction Methods 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 29
- 229920002379 silicone rubber Polymers 0.000 claims description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 26
- 210000004209 hair Anatomy 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 239000003995 emulsifying agent Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- 229910000085 borane Inorganic materials 0.000 claims description 18
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000011782 vitamin Substances 0.000 claims description 15
- 230000001166 anti-perspirative effect Effects 0.000 claims description 14
- 239000003213 antiperspirant Substances 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 14
- 229940088594 vitamin Drugs 0.000 claims description 13
- 229930003231 vitamin Natural products 0.000 claims description 13
- 235000013343 vitamin Nutrition 0.000 claims description 13
- VKPSKYDESGTTFR-UHFFFAOYSA-N 2,2,4,6,6-pentamethylheptane Chemical compound CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 claims description 12
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 12
- 230000008961 swelling Effects 0.000 claims description 12
- 239000003814 drug Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- 239000000344 soap Substances 0.000 claims description 10
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 9
- 239000002304 perfume Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 235000013599 spices Nutrition 0.000 claims description 9
- 239000006210 lotion Substances 0.000 claims description 8
- LSTDYDRCKUBPDI-UHFFFAOYSA-N palmityl acetate Chemical compound CCCCCCCCCCCCCCCCOC(C)=O LSTDYDRCKUBPDI-UHFFFAOYSA-N 0.000 claims description 8
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 7
- 108090000790 Enzymes Proteins 0.000 claims description 7
- 102000004190 Enzymes Human genes 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000006071 cream Substances 0.000 claims description 7
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 7
- BANXPJUEBPWEOT-UHFFFAOYSA-N 2-methyl-Pentadecane Chemical compound CCCCCCCCCCCCCC(C)C BANXPJUEBPWEOT-UHFFFAOYSA-N 0.000 claims description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N isooctadecyl alcohol Natural products CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 claims description 6
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002453 shampoo Substances 0.000 claims description 6
- 230000000475 sunscreen effect Effects 0.000 claims description 6
- 239000000516 sunscreening agent Substances 0.000 claims description 6
- KGKQNDQDVZQTAG-UHFFFAOYSA-N 8-methylnonyl 2,2-dimethylpropanoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)(C)C KGKQNDQDVZQTAG-UHFFFAOYSA-N 0.000 claims description 5
- RVFAFJNKMUHRDO-UHFFFAOYSA-N C(C)C(CC(N)N)(CC)CC.[B] Chemical compound C(C)C(CC(N)N)(CC)CC.[B] RVFAFJNKMUHRDO-UHFFFAOYSA-N 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 5
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 5
- 235000020245 plant milk Nutrition 0.000 claims description 5
- 229960003656 ricinoleic acid Drugs 0.000 claims description 5
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 5
- FLPJVCMIKUWSDR-UHFFFAOYSA-N 2-(4-formylphenoxy)acetamide Chemical compound NC(=O)COC1=CC=C(C=O)C=C1 FLPJVCMIKUWSDR-UHFFFAOYSA-N 0.000 claims description 4
- SFAAOBGYWOUHLU-UHFFFAOYSA-N 2-ethylhexyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(CC)CCCC SFAAOBGYWOUHLU-UHFFFAOYSA-N 0.000 claims description 4
- ODMZDMMTKHXXKA-QXMHVHEDSA-N 8-methylnonyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCCCCCC(C)C ODMZDMMTKHXXKA-QXMHVHEDSA-N 0.000 claims description 4
- 241000195940 Bryophyta Species 0.000 claims description 4
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 4
- SSZBUIDZHHWXNJ-UHFFFAOYSA-N Stearinsaeure-hexadecylester Natural products CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCCCCCCCCCC SSZBUIDZHHWXNJ-UHFFFAOYSA-N 0.000 claims description 4
- 229940048299 acetylated lanolin alcohols Drugs 0.000 claims description 4
- 239000003429 antifungal agent Substances 0.000 claims description 4
- 229940049297 cetyl acetate Drugs 0.000 claims description 4
- 229940074979 cetyl palmitate Drugs 0.000 claims description 4
- 235000005513 chalcones Nutrition 0.000 claims description 4
- 239000008266 hair spray Substances 0.000 claims description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical class CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 4
- PXDJXZJSCPSGGI-UHFFFAOYSA-N hexadecanoic acid hexadecyl ester Natural products CCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC PXDJXZJSCPSGGI-UHFFFAOYSA-N 0.000 claims description 4
- QAKXLTNAJLFSQC-UHFFFAOYSA-N hexadecyl tetradecanoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCC QAKXLTNAJLFSQC-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 229960002725 isoflurane Drugs 0.000 claims description 4
- 235000011929 mousse Nutrition 0.000 claims description 4
- 210000000434 stratum corneum Anatomy 0.000 claims description 4
- DZKXJUASMGQEMA-UHFFFAOYSA-N tetradecyl tetradecanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCC DZKXJUASMGQEMA-UHFFFAOYSA-N 0.000 claims description 4
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 4
- 241001615463 Trichogenes Species 0.000 claims description 3
- 230000001815 facial effect Effects 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 239000000118 hair dye Substances 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000002884 skin cream Substances 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 91
- 239000000047 product Substances 0.000 description 45
- 239000003921 oil Substances 0.000 description 43
- 235000019198 oils Nutrition 0.000 description 43
- 239000002585 base Substances 0.000 description 42
- 229920000642 polymer Polymers 0.000 description 39
- 239000000523 sample Substances 0.000 description 39
- 239000006072 paste Substances 0.000 description 35
- 150000003254 radicals Chemical class 0.000 description 30
- 239000000463 material Substances 0.000 description 27
- 125000000217 alkyl group Chemical group 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- 239000000178 monomer Substances 0.000 description 22
- 239000004743 Polypropylene Substances 0.000 description 21
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 20
- 238000003828 vacuum filtration Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000001993 wax Substances 0.000 description 18
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 17
- 239000004205 dimethyl polysiloxane Substances 0.000 description 17
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 17
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 17
- 239000000843 powder Substances 0.000 description 17
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 16
- 239000013543 active substance Substances 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 16
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 15
- 210000003491 skin Anatomy 0.000 description 15
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- 102100026735 Coagulation factor VIII Human genes 0.000 description 12
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 12
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
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- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 10
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- 150000001412 amines Chemical class 0.000 description 10
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- 125000005702 oxyalkylene group Chemical group 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
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- 125000003118 aryl group Chemical group 0.000 description 9
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- 239000002537 cosmetic Substances 0.000 description 9
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 9
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
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Abstract
In various embodiments, provided are hydrophilically-modified silicone compositions comprising substantially spherical elastomeric microparticles, methods of making such compositions, and silicone pastes, personal care, and healthcare products comprising such silicone compositions.
Description
In a plurality of embodiments, the application relates to and comprises by the silicon-ketone composition of the hydrophilic modifying of the free-radical polymerized elastomer fine particle that forms of organopolysiloxane and organic comonomer and make such method for compositions.
The silicone paste can be characterized as being usually has cross-linked polymer particle matrix (elastomerics) component that is dispersed in the fluid components.Fluid components and elastomerics be sufficiently compatible to be trapped in the matrix to become and to cause the particulate swelling.Found that such silicon-ketone composition is particularly useful in personal care application, this is because it introduces the ability that liquid is given smooth, thread, the low residue sense after drying up simultaneously to skin or hair.Except fluid, portability has other compounds such as activeconstituents in the matrix.So, the silicone paste composition can be used for sealing various active composition such as medicament, VITAMINs, spices, oil and lotion, is used for sending in makeup, personal care and health care products.
In order to attempt solving, developed the method for modified silicone to having the demand with the lasting existence of water, other polar materials and the better consistency of organic cpds, absorption and dispersed silicone.For example, WO 2007/007521A1 instruction uses specific hydrophilic finishing agent to coat the silicone resin surface so that it more can disperse in the aqueous dispersion media of pH 3-13.Yet this method does not cause granule interior hydrophilic, and this makes and is difficult to seal hydrophilic active.In another example, WO 2001/014458 instruction alkenyl-functional silicone compounds, the functional silicone compounds of silyl hydride and one or more allyl groups-initial and with the crosslinked hydrosilylation reactions product of hydrogen, alkyl, aryl or acyl group terminated polyether.Find this silicone elastomer performance stability and with the consistency of polar organic solvent, and the component in the usable as personal care products.Although this method has been set up polar functionality in elastomerics, it has and the relevant inherent limitation of decolouring that suppresses Pt curing catalysts, cost and Pt catalyzer easily.With respect to capable of using but be not suitable for some other organic cpds based on the curing system of hydrosilylation, the suction of unsaturated polyether also is limited slightly.
Preparation silicone elastomer particulate progress recently comprises use radical polymerization.For example; US2008/0085983A1 describes through in the presence of solvent (polymerisate is at the insoluble basically therein fluid of temperature of reaction) or non-solvent (polymerisate is at the insoluble in fact therein fluid of temperature of reaction) for the resulting polymers difference, the radical polymerization or the crosslinked method for preparing polymer beads of organo-borane-amine compound-catalytic organic or an organosilane monomer, oligopolymer and/or polymkeric substance.Yet paste, its preparation method or its that such method does not have instruction to comprise the particulate of hydrophilic modifying are used to send the purposes of personal care or health care activeconstituents.Therefore, still exist in this area such paste, the demand of methods and applications.Also exist in this area having but do not suffer the curing of known compositions to suppress the demand with other circumscribed silicone pastes with water wetted material enhanced consistency.
These demands are satisfied with the such method for compositions of manufacturing by the silicon-ketone composition of hydrophilic modifying provided by the invention.According to some embodiments, the silicone paste that comprises by the free-radical polymerized elastomer fine particle of spheric basically that forms of organopolysiloxane and organic comonomer is provided, wherein the silicone particulate of gained is soluble in some non-solvent.But when in being dispersed in absorption fluids (absorbable fluid), forming paste; Such elastomerics swelling forms spheric swelling particulate basically; It can be used for multiple application, includes but not limited to, sends the activeconstituents that is used for personal care and health care products.
According to a plurality of embodiments, the silicon-ketone composition of hydrophilic modifying is by comprising following method preparation: polymeric component (A), at least a organopolysiloxane with at least two radical polymerizable groups of average per molecule; And component (B), at least a organic comonomer with at least one radical polymerizable groups of average per molecule; The existence that wherein is aggregated in following component takes place down: component (C), at least a organo-borane radical initiator; Component (D) is with the immiscible at least a non-solvent of component (A); Randomly, component (E), at least a organonitrogen reactive compounds; And oxygen, keep simultaneously from about 5 ℃ of silicone elastomer particulates that are formed on insoluble hydrophilic modifying the component (D) to about 95 ℃ temperature.In a plurality of embodiments, form paste but reclaim the silicone elastomer particulate and it is dispersed at least a absorption fluids.
Of the present invention these will become obvious with other characteristics and benefit during following detailed description.
With obtaining easily to the understanding more completely of the present invention and its many embodiments because they when the associating accompanying drawing is considered through the understanding that improves with reference to following detailed description, in the accompanying drawings:
Fig. 1 is PDMS and the HEMA copolymerization particulate details in a play not acted out on stage, but told through dialogues STEM image of embodiment 7, and wherein the zone (pHEMA) of light density shows than dark contrast (darker contrast);
Fig. 2 is PDMS and the HEMA copolymerization particulate light field TEM image of embodiment 7, and wherein the zone of higher density (PDMS) shows than dark contrast;
Fig. 3 comprises the particulate TEM image that gathers (dimethyl siloxane-be total to-NSC 11448) for preparing with the mode that is similar to embodiment 20; Be to be rich in organic aqueous favoring wherein and be the hydrophobic phase that is rich in silicon, and wherein to be separated be not have macroface to separate in the rank of 100nm than dark areas than bright area;
Fig. 4 shows that wherein the monomeric starting point concentration of IPAA changes from 0-80wt% from the thermogravimetric analysis of the polymer beads that gathers (dimethyl siloxane-be total to-NSC 11448) comprising of embodiment 23;
Fig. 5 shows that wherein the monomeric starting point concentration of IPAA changes from 0-80wt% from the ATR-IR spectrum of the polymer beads that gathers (dimethyl siloxane-altogether-NSC 11448) comprising of embodiment 23, and wherein acid amides I (at 1640cm
-1) and acid amides II (1550cm
-1) peak shows the corresponding increase that gathers (N-NSC 11448) in the polymer beads;
Fig. 6 shows that wherein the monomeric starting point concentration of IPAA changes from 0-50wt% from the DSC of the polymer beads that gathers (dimethyl siloxane-be total to-NSC 11448) comprising of embodiment 20 and 23; Along with the amount increase of IPAA, endotherm(ic)peak (at 50 ℃) area reduces, and indication gathers (n-NSC 11448) and replaced some siloxanes.
To describe characteristic of the present invention and benefit now, and mention specific embodiments once in a while.Yet the present invention can multi-formly realize, and should not be interpreted as the embodiment that is limited to this paper elaboration.But, these embodiments are provided so that present disclosure fully with complete and will more fully pass on scope of the present invention to those skilled in the art.
Except as otherwise noted, otherwise all T.T.s that this paper uses and scientific terminology have the identical implication of implication with those skilled in the art institute common sense.Used term only was in order to describe particular during this paper described, and was restrictive unexpectedly.Only if context clearly indicates in addition, otherwise as used in specification sheets and the accompanying claims, singulative " (a) ", " one (an) " and " being somebody's turn to do (the) " mean and also comprise plural form.
Only if context clearly indicates in addition, otherwise " be independently selected from ", mean and be meant that the group of mentioning can be identical, different or its mixed form like term used in specification sheets and the accompanying claims.Therefore, under this definition, phrase " X
1, X
2And X
3Be independently selected from rare gas element and " will comprise following situation: X wherein
1, X
2With X
3All identical, X wherein
1, X
2With X
3All inequality and X wherein
1With X
2Identical but X
3Different.
As term used in specification sheets and the accompanying claims " but absorption fluids " mean be meant sufficiently compatible with the elastomerics of gained with as absorbed polarity of thinner or non-polar fluid.In some embodiments, but absorption fluids can be, but do not require and be, immiscible with water.The fluidic instance that is fit to polymeric system is found in the standard polymers handbook, and such as Polymer Handbook, the third edition is edited by J.Brandrup and E.H.Immergut, John Wiley & Sons, VII/379-382+ page or leaf, (1989).
Like the term " viscosity " of relevant paste used in specification sheets and the accompanying claims, mean the value (η ') of the real component that is meant the complex viscosity of measuring with rheometer.The instance of the rheometer that is fit to includes but not limited to, Rheometrics RDA II parallel-plate rheometer uses the radian frequency of small strain power oscillatory shear experiment (small strain dynamic oscillatory shear experiment) with 10rad/s; With the Brookfield DV-II+ rheometer that has Helipath annex and T-D axle (20.4mm cross bar),, follow the testing sequence of manufacturers suggestion and 25 ℃ of measurements with 2.5rpm.η ' is the material function that is independent of method, as long as use comparable test frequency and strain rate.For simple aggregation thing and fluid; Such as the independent component that constitutes elastic composition, " viscosity " is meant the zero-shear viscosity with the extrapolation that is relatively independent of shearing rate of in small strain power oscillatory shear experiment, measuring for the enough low shearing rate of η '.For paste, " viscosity " among the application's the embodiment is meant the η ' value of measuring with the frequency of indication and strain rate.
Mean like term used in specification sheets and the accompanying claims " spheric basically " and to be meant absolute sphere and mainly to be spherical.Therefore, phrase " spheric particle basically " means and contains (or main) the separately particle that has spheric form basically but slight deviations is arranged.This phrase also means contains the sample that has than the more spheroidal particle of aspherical particle.
Except as otherwise noted, otherwise be interpreted as in all scenario, being modified by term " about " like all numbers of the amount of expression composition used in specification sheets and the claim, characteristic such as molecular weight, reaction conditions or the like.Therefore, except as otherwise noted, otherwise be approximation like numerical characteristic listed in specification sheets and the claim, it can depend on attempts the desired characteristic that obtains and changes in embodiment of the present invention.Although setting forth the numerical range and the parameter of wide region of the present invention is approximation, the numerical value of in specific embodiment, setting forth is by report as far as possible exactly.Yet, any numerical value comprise inherently by the error that in its corresponding measuring method, runs into some error that must cause.
Except other, this paper provides and comprises by the such method for compositions of the silicon-ketone composition of the free-radical polymerized hydrophilic elastomer fine particle of spheric basically that forms of organopolysiloxane and organic comonomer, preparation and comprise the personal care and the health care products of such compsn.In some embodiments, the silicone elastomer of hydrophilic modifying is formed by emulsion polymerisation process.
Through radical technology letex polymerization monomer is known in the art.For example; Kim equals J.Am.Chem.Soc.2006; 128; Among the 6570-6571; Show through transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) that polymeric methyl acrylate, TEB 3K or vinyl acetate monomer form the rubber fruit shape diphase particles with two semisphere lobes in the seed latex particle of the YSR 3286 in being suspended in water, this diphase particles is by the generation that is separated of polymeric propenoate with wide relatively interface and YSR 3286 integral part.This points out some multipolymer solublizations, and one of its mesopetalum has basically no silicone, thereby makes particle discontinuous in silicone.Yet do not have known indication in this area: the elastomer fine particle with spheric basically even, silicone phase continuously, overall homogeneous can form in emulsion through free-radical polymerized method.And; Do not have known indication in this area: through with silicone monomer and Acrylic Acid Monomer based on the free-radical polymerized product of emulsion and paste that silicone-compatible solvents combination is obtained performance is similar to the physical property based on the paste of silicone of hydrosilylation cure, also allow the absorption of enhanced polarity material simultaneously.
In a plurality of embodiments, the method for the silicon-ketone composition of preparation hydrophilic modifying is provided.Such method comprises polymeric component (A), at least a organopolysiloxane with at least two radical polymerizable groups of average per molecule; And component (B), at least a organic comonomer with at least one radical polymerizable groups of average per molecule; The existence that wherein is aggregated in following component takes place down: component (C), at least a organo-borane radical initiator; Component (D) is with the immiscible at least a non-solvent of component (A); Randomly, component (E), at least a organonitrogen reactive compounds; Randomly, component (F) is applicable at least a activeconstituents of personal care and health care products; Randomly, component (G), at least a emulsifying agent; And oxygen, keep simultaneously from about 5 ℃ of silicone elastomer particulates that form hydrophilic modifying to about 95 ℃ temperature.In some embodiments, but the insoluble silicone elastomer particulate of recyclable formation and it is dispersed at least a absorption fluids forms paste.In some embodiments, but absorption fluids absorbed by particulate and form spheric swelling silicone particles basically.
In some embodiments, the silicone elastomer particulate is through forming to dispersion-s that comprises component (A), component (B), component (D) and component (E) or emulsion adding component (C).In some embodiments, the silicone elastomer particulate is through forming to dispersion-s that comprises component (A), component (B), component (C) and component (D) or emulsion adding component (E).According to a plurality of embodiments, the paste that comprises through the silicone elastomer particulate that comprises the hydrophilic modifying that following method prepares is provided: (I) polymeric component (A) and component (B) in the presence of following component: component (C); Component (D); Randomly, component (E); Randomly, component (F); Randomly, component (G); And oxygen, keep simultaneously from about 5 ℃ of silicone elastomer particulates that are formed on insoluble hydrophilic modifying the component (D) to about 95 ℃ temperature; But (II) reclaim silicone elastomer particulate and they are dispersed at least a absorption fluids.
Component (A), the polymerisable organopolysiloxane of radical
Usually, component (A) comprises the organopolysiloxane with radical polymerizable moiety; Silicone resin; Or its combination.Said organopolysiloxane can be polymeric or oligopolymer and mixture of polymers, and the polymerization organopolysiloxane can be homopolymerization or assorted gathering.In addition, the structure of organopolysiloxane can be straight chain, side chain or hyperbranched.Radical-catalytic the addition polymerization of component (A) experience, and in some embodiments, can also experience copolymerization and/or crosslinked.
In some embodiments, component (A) comprises the organopolysiloxane with at least two radical polymerizable moieties of per molecule, and wherein such part is simple function, polyfunctional or its combination.Therefore, component (A) can be the mixture at the different organopolysiloxane of the properties of its functionality and/or radical polymerizable moiety.The organopolysiloxane of component (A) also can be aspect denseness from the change of fluid to natural gum.For example, organopolysiloxane can be fluid, solid or shear the flowable solid that becomes at high temperature or through applying.In some embodiments, organopolysiloxane have 25 ℃ from about 1cP to about 5,000,000cP; Alternatively, 25 ℃ from about 50cP to about 500,000cP; Alternatively, 25 ℃ from about 100cP to about 100, the viscosity of 000cP.
The organopolysiloxane of component (A) also can have second-order transition temperature, or forms the particle with second-order transition temperature in polymerization or crosslinked back, the wherein silicon-ketone composition of gained experience noticeable change aspect its viscosity under use temperature.Such compsn especially can be used for sealing through introducing the activeconstituents that heat discharges.
In some embodiments, component (A) can comprise having the polymerisable organopolysiloxane of the radical that is selected from following formula:
(1)R
1 3SiO(R
1 2SiO)
a(R
1R
2SiO)
bSiR
1 3;
Wherein a has zero value and b to 20,000 and has 1 to 20,000 value; And each R wherein
1Group is hydrogen, halogen or unit price organic group independently, and each R
2Group is the unsaturated organic group of unit price independently; With
(2)R
3 2R
4SiO(R
3 2SiO)
c(R
3R
4SiO)
dSiR
3 2R
4;
Wherein c has zero value and d to 20,000 and has zero to 20,000 value; And each R wherein
3Be hydrogen, halogen or unit price organic group independently, and each R
4Group is the unsaturated organic group of unit price independently.
The R that is fit to
1And R
3Group includes but not limited to, hydrogen; Organic group (straight chain and/or side chain) is such as alkyl, haloalkyl, thiazolinyl, alkynyl, acrylate-functional groups and methacrylate functional; With other organo-functional groups such as glycidyl, amido, ether, cyanate ester based, isocyano-, ester group, carboxylic acid group, carboxylate group, succsinic acid ester group, anhydride group, sulfydryl, thioether group, azido-, phosphonate group, phosphino-, the isocyano-of sheltering and hydroxyl.Such examples of groups includes but not limited to, acrylic-functional is such as acryloxy propyl group and methacryloxypropyl; Alkyl is such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl and the tertiary butyl; Thiazolinyl is such as vinyl, allyl group and crotonyl; Alkynyl is such as ethynyl and proyl; Aromatic group is such as phenyl, tolyl and xylyl; The cyanic acid alkyl is such as cyano ethyl and cyanic acid propyl group; The halogenation alkyl, such as 3,3,3-trifluoro propyl, 3-chloropropyl, dichlorophenyl and 6,6,6,5,5,4,4,3,3-nine fluorine hexyls; Alkenyloxy gathers (oxy alkylene) group, gathers (oxypropylene) and allyloxy-gather (oxypropylene)-be total to-gather (oxygen ethene) base such as allyloxy (T 46155), allyloxy; Alkoxyl group gathers (oxy alkylene) group, gathers (oxypropylene) and propoxy--gather (oxypropylene)-be total to-gather (oxygen ethene) group such as propoxy-(T 46155), propoxy-; The substituted alkoxyl group of halogen gathers (oxy alkylene) group, gathers (oxypropylene) and perfluor propoxy--gather (oxypropylene)-be total to-gather (oxygen ethene) group such as perfluor propoxy-(T 46155), perfluor propoxy-; Alkoxyl group is such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy and ethyl hexyl oxy; Aminoalkyl group is such as 3-aminopropyl, the amino hexyl of 6-, the amino undecyl of 11-, 3-(N-allyl amino) propyl group, N-(2-amino-ethyl)-3-aminopropyl, N-(2-amino-ethyl)-3-aminoisobutyric base, p-aminophenyl, 2-ethyl pyridinyl and 3-propyl pyrrole base; Epoxy alkyl is such as 3-glycidoxypropyl, 2-(3,4 ,-epoxycyclohexyl) ethyl and 5,6-epoxy hexyl; Ester functional group is such as acetoxyl group ethyl and benzoyloxy group propyl group; Hydroxy functional group is such as hydroxyl and 2-hydroxyethyl; Isocyanic ester and the isocyanate functional group who shelters are such as 3-isocyanato propyl group, three-3-propyl group isocyanuric acid ester group, propyl group-tertiary butyl carbamate groups and propyl group ethyl carbamate base; Aldehyde functional group is such as undecyl aldehyde base and butyraldehyde base; The anhydride functional group is such as 3-propyl group succinyl oxide base and 3-propyl group maleic anhydride base; Carboxylic acid functional is such as 3-carboxyl propyl group and 2-carboxy ethyl; And the metal-salt of carboxylic acid, such as zinc, sodium or the sylvite of 3-carboxyl propyl group and 2-carboxy ethyl.
The R that is fit to
2And R
4Group includes but not limited to have the unit price thiazolinyl and the alkynyl of 2-12 carbon atom, such as vinyl, allyl group, crotonyl, ethynyl and proyl; Alkenyloxy gathers (oxy alkylene) group, gathers (oxypropylene) and allyloxy-gather (oxypropylene)-be total to-gather (oxygen ethene) group such as allyloxy (T 46155), allyloxy; Acrylic-functional is such as acryloxy propyl group and methacryloxypropyl; With its halogen-substituted analogue.In certain embodiments, R
2And R
4Be selected from acrylate-based and methacrylate based.
Some representative example of component (A) include but not limited to, the end capped YSR 3286 of methacryloxypropyl dimethylsilane oxygen base; The end capped YSR 3286 of acryloxy propyl-dimethyl siloxy-, 1; Two (methacryloxypropyl) tetramethyl disiloxanes, 1 of 3-; Two (acryloxy propyl group) tetramethyl disiloxanes, 1 of 3-; Two (methacryloxy methyl) tetramethyl disiloxanes, 1 of 3-; Two (acryloyl-oxy ylmethyl) tetramethyl disiloxanes of 3-, α; The end capped YSR 3286 of YSR 3286, methacryloxypropyl, the α of
methacryloxy methyl dimethoxy base silyl terminated; YSR 3286, the end capped YSR 3286 of methacryloxypropyl dimetylsilyl, the α of
acryloxy methyl dimethoxy base silyl terminated; YSR 3286, side chain propenoate and the functional polymkeric substance of methacrylic ester of
acryloxy propyl-dimethyl silyl terminated are such as gathering (acryloxy propyl group-methyl-silicane oxygen base) YSR 3286 and gathering (methacryloxypropyl-methyl-silicane oxygen base) polydimethylsiloxanecopolymer copolymer; Telechelic YSR 3286 with a plurality of propenoate or methacrylate functional comprises those that form to the Michael reaction of the end capped YSR 3286 of amine via multiple propenoate or multiple methacrylate monomers; With its combination.Also be suitable for as the propenoate that comprises simple function of the polymerisable silicoorganic compound of radical or the organopolysiloxane of methacrylate-terminated, such as an end by methyl acryloxy propyl-dimethyl silyl terminated and the other end by the end capped YSR 3286 of normal-butyl dimetylsilyl.
In some embodiments, component (A) can comprise having the silicone resin that is independently selected from following organopolysiloxane structural unit:
Wherein M represents the simple function unit R
3SiO
1/2D represents two functional unit R
2SiO
2/2T represents trifunctional units RSiO
3/2And Q represents four functional unit SiO
4/2
In some embodiments, component (A) can comprise being selected to have R
5 3SiO
1/2Unit and SiO
4/2Unitary MQ resin; Has R
5SiO
3/2Unit and R
5 2SiO
2/2Unitary TD resin; Has R
5 3SiO
1/2Unit and R
5SiO
3/2Unitary MT resin; Has R
5 3SiO
1/2Unit, R
5SiO
3/2Unit and R
5 2SiO
2/2The silicone resin of unitary MTD resin and its combination; Each R wherein
5Group is the unit price organic group that has from 1-20 carbon atom independently.In some embodiments, R
5Have from 1-10 carbon atom.In some embodiments, at least one R
5Group is the polymerisable unsaturated organic group of radical.
R
5Suitable instance include but not limited to that acrylate-functional groups is such as acryloxyalkyl; Methacrylate functional is such as the methacryloxy alkyl; Cyano functional group; Univalence hydrocarbyl; With its combination.Univalence hydrocarbyl can comprise alkyl, such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, amyl group, neo-pentyl, octyl group, undecyl and octadecyl; Naphthenic base is such as cyclohexyl; Thiazolinyl is such as vinyl, allyl group, crotonyl and hexenyl; Alkynyl is such as ethynyl, proyl and butynyl; Aryl is such as phenyl, tolyl, xylyl, benzyl and 2-styroyl; The halogenation alkyl, such as 3,3,3-trifluoro propyl, 3-chloropropyl, dichlorophenyl and 6,6,6,5,5,4,4,3,3-nine fluorine hexyls; With its combination.Cyano functional group can comprise the cyanic acid alkyl, such as cyano ethyl and cyanic acid propyl group and combination thereof.
R
5Can comprise that also alkoxyl group gathers (oxy alkylene) group, gather (oxypropylene) and propoxy--gather (oxypropylene)-be total to-gather (oxygen ethene) group such as propoxy-(T 46155), propoxy-; The substituted alkoxyl group of halogen gathers (oxy alkylene) group, gathers (oxypropylene) and perfluor propoxy--gather (oxypropylene) copolymerization (oxygen ethene) group such as perfluor propoxy-(T 46155), perfluor propoxy-; Alkenyloxy gathers (oxy alkylene) group, gathers (oxygen ethene), allyloxy such as allyloxy and gathers (oxypropylene) and allyloxy-gather (oxypropylene) copolymerization (oxygen ethene) group; Alkoxyl group is such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy and ethyl hexyl oxy; Aminoalkyl group is such as 3-aminopropyl, the amino hexyl of 6-, the amino undecyl of 11-, 3-(N-allyl amino) propyl group, N-(2-amino-ethyl)-3-aminopropyl, N-(2-amino-ethyl)-3-aminoisobutyric base, p-aminophenyl, 2-ethyl pyridinyl and 3-propyl pyrrole base; The aminoalkyl group that is hindered is such as tetramethyl-piperidyl oxygen propyl group; Epoxy alkyl is such as 3-glycidoxypropyl, 2-(3,4 ,-epoxycyclohexyl) ethyl and 5,6-epoxy hexyl; Ester functional group is such as acetoxy-methyl and benzoyloxy group propyl group; Hydroxy functional group is such as hydroxyl and 2-hydroxyethyl; Isocyanic ester and the isocyanate functional group who shelters are such as 3-isocyanato propyl group, three-3-propyl group isocyanuric acid ester group, propyl group-tertiary butyl carbamate groups and propyl group ethyl carbamate base; Aldehyde functional group is such as undecyl aldehyde base and butyraldehyde base; The anhydride functional group is such as 3-propyl group succinyl oxide base and 3-propyl group maleic anhydride base; Carboxylic acid functional is such as 3-carboxyl propyl group, 2-carboxy ethyl and 10-carboxy decyl; The metal-salt of carboxylic acid is such as zinc, sodium or the sylvite of 3-carboxyl propyl group and 2-carboxy ethyl; With its combination.
Some specific exampless that can be used as the silicone resin that is fit to of component (A) include but not limited to M
The methacryloxy methylThe Q resin; M
MethacryloxypropylThe Q resin; MT
The methacryloxy methylThe T resin; MT
Methyl-prop Alkene acyloxy propyl groupThe T resin; MDT
The methacryloxy methylT
PhenylThe T resin; MDT
MethacryloxypropylT
PhenylThe T resin; M
VinylT
PhenylResin; TT
The methacryloxy methylResin; TT
MethacryloxypropylResin; T
PhenylT
Methacryloxy MethylResin; T
PhenylT
MethacryloxypropylResin; TT
PhenylT
The methacryloxy methylResin; TT
PhenylT
Methacryloxypropyl Base thirdThe base resin; With its combination.
Silicone resin can be through any method preparation known in the art.In some embodiments, resin is through being made by the resin copolymer that silica hydrosol adds the generation of cap method with the capping reagent processing that comprises thiazolinyl.This is preferably incorporated under the acidic conditions silica hydrosol and hydrolyzable three organosilanes such as trimethylchlorosilane, siloxanes such as SWS-F 221 and its composite reaction and reclaims the multipolymer that has M and Q group, comprises 2 to 5%wt hydroxyls then.Can with multipolymer with comprise that the undersaturated end-capping reagent of the end-capping reagent of unsaturated organic group and not fatty family is to be enough in resin, to provide the quantitative response with respect to M, D or the T group of the unsaturated organic functional of 3 to 30 molar percentages of all M, D, T and the unitary summation of Q of formation resin.The end-capping reagent that is fit to comprises silazane, siloxanes, silane and its combination.
In some embodiments, component (A) be selected from acrylate-functional with functional YSR 3286 of methacrylic ester and resin.Realized good result through the YSR 3286 of selection methacrylate-terminated and the YSR 3286 of acrylate ended.
Component (B), polymerisable comonomer
Usually, component (B) comprises at least a organic comonomer that can radical polymerization.In some embodiments, component (B) is the organic comonomer with at least one radical polymerizable groups of per molecule.In some embodiments, organic comonomer of component (B) has at least one hydrophilic radical of per molecule.The instance of the organic cpds that is fit to includes but not limited to; 2-EHA, methylacrylic acid 2-ethylhexyl, methacrylic ester, TEB 3K, diacrylic acid pentyl diol ester, dimethacrylate DOPCP, glycidyl acrylate, SY-Monomer G, allyl acrylate, allyl methacrylate(AMA), stearyl acrylate alcohol ester, methylacrylic acid tetrahydrofuran ester, vinylformic acid caprolactone, vinylformic acid perfluor butyl ester, methylacrylic acid perfluor butyl ester, vinylformic acid 1H; 1H; 2H; 2H-17 fluorine esters in the last of the ten Heavenly stems, methylacrylic acid 1H; 1H; 2H, 2H-17 fluorine esters in the last of the ten Heavenly stems, tetrahydrochysene perfluorinated acrylate, phenoxyethyl acrylate, methylacrylic acid ethyl phenoxy, vinylformic acid dihydroxyphenyl propane ester, dimethacrylate dihydroxyphenyl propane ester, vinylformic acid ethoxylation dihydroxyphenyl propane ester, methylacrylic acid ethoxylation dihydroxyphenyl propane ester, diacrylate hexafluoro bisphenol-a ester, dimethacrylate hexafluoro bisphenol-a ester, diacrylate glycol ether ester, dimethacrylate glycol ether ester, dipropylene glycol diacrylate, dipropyleneglycol dimethacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, W 166 methacrylic ester, polypropyleneglycol diacrylate, polypropylene glycol dimethacrylate, monomethyl vinylformic acid propylene glycol ester, monomethyl vinylformic acid glycol ester, N-NSC 11448, Viscoat 295, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, pentaerythritol triacrylate, trimethylammonium vinylformic acid pentaerythritol ester, pentaerythritol tetracrylate, pentaerythritol tetramethacrylate, 3-M Cr, carbonic acid allyl group methyl esters, coke diallyl phthalate, acetoacetic acid allyl ester, carbonic acid diallyl, Phthalic acid, diallyl ester, dimethyl itaconate, carbonic acid diallyl or its combination.Other available organic cpds comprise, the polyisobutene of the rubber-like oligopolymer that terminal polyester-urethane prepolymer, (methyl) propenoate of (methyl) propenoate that prepare through the prepolymer reaction with isocyanate-reactive acrylate monomer, oligopolymer or polymkeric substance such as crylic acid hydroxy ester and isocyanate-functional is terminal and the polyisobutene of polymkeric substance such as propenoate end or methacrylic ester end and the natural oil derivatives of (methyl) acrylate functional are such as methacrylate functionalized VT 18.Those skilled in the art will recognize that, except other factor, will depend on the intended use of product of character and the gained of component (A) to the selection of the organic cpds that is used for component (B).
In some embodiments, component (B) can be organic acid (for example a, vinylformic acid).When component (B) when being organic acid, this acid also can be used as the organonitrogen reactive compounds.
Although many organic comonomers are suitable as component (B); But through selecting TEB 3K, stearyl methacrylate, n-butyl acrylate, methylacrylic acid 2-hydroxyl ethyl ester, methylacrylic acid benzene methyl, methylacrylic acid tetrahydrofuran ester, dimethylaminoethyl methacrylate, N, N-DMAA, n-vinyl formamide, 4-vinylpridine, l-vinyl-2-pyrrolidone and N-NSC 11448 have obtained good result as component (B).
In some embodiments, component (B) be silicon-ketone composition from about 0.1% to about 50% (by weight); Alternatively, silicon-ketone composition from about 1% to about 40% (by weight); Alternatively, silicon-ketone composition from about 2.5% to about 25% (by weight).
Component (C), the organo-borane radical initiator
Usually, component (C) comprises and can produce radical and cause radical addition polymerization and/or crosslinked at least a organoborane compounds.Can use and cause the organoborane compounds of organo-borane in the non-hypergolic stabilization of envrionment conditions.In some embodiments; Component (C) is a mixture; This mixture is between the stable organonitrogen (for example, amine) that is fit to of envrionment conditions, to form with causing mixture at organo-borane, is wherein producing radical (and initiated polymerization) behind the introducing organonitrogen reactive compounds in the presence of the oxygen.In some embodiments, component (C) is the organoborane compounds that wherein after heating, produces radical (and initiated polymerization).In some embodiments, component (C) is the organo-borane (for example, the solution of trialkylborane among the THF) of solvent-stabilization, thereby wherein allows solvent evaporation to discharge borine and to produce radical.
In some embodiments, component (C) is the organo-borane-organonitrogen mixture that can be selected from the mixture with following formula:
Wherein on behalf of boron and N, B represent nitrogen; Wherein at least one among R6, R7 and the R8 comprises one or more Siliciumatoms, and wherein siliceous group is covalently attached to boron; Wherein R6, R7 and R8 can be independently selected from following group: have on hydrogen, naphthenic base, the main chain straight or branched of 1-12 carbon atom alkyl, alkaryl, organosilicon alkyl such as alkyl tin groups, alkyl silane groups or aryl-silane base, organo-siloxane base, can conduct with the acting alkylidene group of covalency bridge of another boron atom, can conduct and the covalency bridge acting divalence organo-siloxane base or the substituted homologue of its halogen of another boron atom; Wherein R9, R10 and R11 be produce can with the group of boron compound amine compound or polyamino compound, and be independently selected from hydrogen, contain the alkyl or the organosilicon functional group of the substituted 1-10 of containing of alkyl, a halogen carbon atom of 1-10 carbon atom; And wherein at least two at least two in R6, R7 and the R8 group and R9, R10 and the R11 group can be combined to form heterocycle structure, condition be from the atomicity of two combination groups be no more than 11.
In some embodiments, component (C) can be selected from alkyl borane-organonitrogen mixture, and it includes but not limited to, comprises to have formula BR "
3Trialkylborane-organonitrogen mixture, the wherein R of trialkylborane " representative comprises the straight chain of 1-20 carbon atom and the aliphatics or the aromatic hydrocarbyl of side chain.The instance of the trialkylborane that is fit to includes but not limited to trimethylammonium borine, three normal-butyl borines, three n-octyl borines, three sec.-butyl borines, three (dodecyl) borines and diethylamino phenyl base borine.
The instance of the organonitrogen that is fit to that is used to form the organo-borane-organonitrogen mixture of component (C) includes but not limited to 1,3 tn; 1, the 6-hexanediamine; Methoxy propanamine; Pyridine; Isophorone diamine; With siliceous amine, such as 3-TSL 8330,3-aminopropyltriethoxywerene werene, 2-(trimethoxysilylethylgroup group) pyridine, aminopropyl silantriol, 3-(m-aminophenyl oxygen base) propyl trimethoxy silicane, 3-aminopropyl di-isopropyl methoxy silane, aminophenyl Trimethoxy silane, 3-aminopropyl three (methoxy ethoxy) silane (3-aminopropyltris (methoxyethoxethoxy) silane), N-(2-amino-ethyl)-3-TSL 8330, N-(the amino hexyl of 6-) amino methyl Trimethoxy silane, the amino undecyl Trimethoxy silane of N-(2-amino-ethyl)-hI-, (aminoethylamino methyl) mountain Yu base Trimethoxy silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-aminoisobutyric ylmethyl dimethoxy silane and (3-trimethoxy-silylpropyl) diethylidene-triamine.
In some embodiments, the nitrogenous compound that can be used for forming the organo-borane-organonitrogen mixture of component (C) can be selected from the organopolysiloxane with at least one amine functional group.The instance of the amine functional group that is fit to includes but not limited to, 3-aminopropyl, the amino hexyl of 6-, the amino undecyl of 11-, 3-(N-allyl amino) propyl group, N-(2-amino-ethyl)-3-aminopropyl, N-(2-amino-ethyl)-3-aminoisobutyric base, p-aminophenyl, 2-ethylpyridine and 3-propyl pyrrole.Such organopolysiloxane includes but not limited to, has those of the formula that is similar to above-mentioned formula (1) and (2).Other nitrogenous compounds that can be used for forming the organo-borane-organonitrogen mixture of component (C) include but not limited to; N-(3-triethoxysilylpropyltetrasulfide)-4,5-glyoxalidine, urea groups propyl-triethoxysilicane, have the siloxanes of the formula that is similar to above-mentioned formula (1) and (2) and wherein at least one group be the organopolysiloxane resins of imidazoles, amidine or urea/ureido functional group.
In some embodiments, through heating organoborane compounds (preferably organo-borane-organonitrogen mixture) or only the alkyl borane through component (C) that anaerobism ground is comprised be exposed to air, produce radical and initiated polymerization and/or crosslinked.In some embodiments, the organo-borane-organonitrogen mixture through heat contents (C) produces radical and initiated polymerization and/or crosslinked, and wherein heating causes the mixture disassociation.In some embodiments; Organonitrogen reactive compounds through combination partner in oxygen atmosphere (E) [or in some embodiments; Organonitrogen reactive component (B)] with the organo-borane-organonitrogen mixture of component (C); Produce radical and initiated polymerization and/or crosslinked, wherein this combination causes the mixture disassociation.About the latter, can be in the temperature of the dissociation temperature that is lower than organo-borane-organonitrogen mixture, such as produce radical in envrionment temperature or below the envrionment temperature.
Although the organoborane compounds of organonitrogen-stabilization is particularly useful as component (C), it will be understood by those skilled in the art that and to use any organo-borane.The instance that can be used for the alternative stabilized form of organo-borane of the present invention comprises the compound that encircles stabilization such as 9-BBN, or solvent compound organo-borane such as trialkylborane-THF solution.
In some embodiments, component (C) is trialkylborane-organonitrogen mixture, and wherein trialkylborane is selected from boron triethyl, three normal-butyl borines, three n-octyl borines, three sec.-butyl borines and three (dodecyl) borine.Through selecting boron triethyl-propanediamine (TEB-PDA) mixture, boron triethyl-NSC 158165 (TEB-BI) mixture and boron triethyl-methoxy propanamine (TEB-MOPA) mixture and three normal-butyl methoxy propanamines to obtain good result.
Component (D), non-solvent
Usually, component (D) comprises and the immiscible at least a non-solvent of component (A).In some embodiments, component (D) is sufficiently incompatible with the silicone elastomer that polymerization through other components forms, with cause this elastomerics by component D swelling seldom or not by component D swelling.In some embodiments, component (D) is selected from water, acetone and lower alcohol such as methyl alcohol or its combination.
Optional components (E), the organonitrogen reactive compounds
Usually; Optional components (E) comprises at least a organonitrogen reactive compounds; When it makes up and be exposed to oxygenated environment at the organo-borane-organonitrogen mixture with component (C), can cause organo-borane-organonitrogen mixture disassociation, thereby cause radical polymerization and/or crosslinked.The existence of such organonitrogen reactive compounds allows under the temperature of the dissociation temperature of the organo-borane that is lower than component (C)-organonitrogen mixture, to take place fast polymerization and/or crosslinked, and this temperature is included in room temperature and below the room temperature.
Some instances of the organonitrogen reactive compounds that is fit to of component (E) include but not limited to mineral acid, Lewis acid, carboxylic acid, carboxylic acid derivative such as acid anhydrides and succinate, carboxylic metallic salt, isocyanic ester, aldehyde, epoxide, chloride of acid and SULPHURYL CHLORIDE, acetate, vinylformic acid, methylacrylic acid, ROHM, polymethyl acrylic acid, methacrylic anhydride, undecylenic acid, oleic acid, Triple Pressed Stearic Acid, Hydrocerol A, levulinic acid, vinylformic acid 2-carboxyl ethyl ester, isoflurane chalcone diisocyanate monomer or oligopolymer, methacryloyl based isocyanate, etheric acid 2-(methacryloxy) ethyl ester, undecylene aldehyde and dodecyl succinic anhydride.In some embodiments, component (B) can be also to be the organic acid of organonitrogen reactive compounds.For example, vinylformic acid can be used as organic comonomer and organonitrogen reactive compounds the two.
In addition, the organosilane or the organopolysiloxane that have an organonitrogen reactive group can be suitable for component (E).Such compound includes but not limited to, 3-isocyanato propyl trimethoxy silicane; The 3-glycidoxypropyltrimewasxysilane; Straight chain, side chain, arborescens and hyperbranched organopolysiloxane that the propyl group succinyl oxide is functionalized; The functional straight chain of cyclohexene anhydrides, arborescens and hyperbranched organopolysiloxane; Carboxylic acid functionalized straight chain, side chain, arborescens and hyperbranched organopolysiloxane are such as the end capped oligomeric or polymeric YSR 3286 of carboxy decyl; With aldehyde-functionalized straight chain, side chain, arborescens and hyperbranched organopolysiloxane, such as the end capped oligomeric or polymeric YSR 3286 of undecylene aldehyde.
Other organonitrogen reactive compounds that are fit to that are used for component (E) are silicon-containing compounds, and it discharges acid when being exposed to moisture, and this acid causes the organo-borane-organonitrogen mixture disassociation of component (C).Such compound includes but not limited to, ester, the chloride of acid siloxanes of halogenated silanes, acid anhydrides (carboxylic acid) siloxanes, acetoxyl group siloxanes (such as ethyl triacetyl oxygen radical siloxane and methyl triacetyl oxygen radical siloxane), alkyl silicic acid, carboxylic acid and silanol.
The other instance that can be used for the compound of component (E) is when being exposed to uviolizing, to produce those of organonitrogen reactive group, such as containing [SbF
6]
-The salt compounded of iodine of counter ion.About such compound, comprise that also light-sensitive compound such as isopropyl thioxanthone can be useful.
Those skilled in the art will recognize that, except other factor, will depend on the character of component (C) to the selection of the organonitrogen reactive compounds that is used for component (E).YSR 3286 through selecting acetate, vinylformic acid, isoflurane chalcone diisocyanate and carboxy blocking has obtained good result as component (E).
When in silicon-ketone composition, using the organonitrogen reactive compounds, free-radical generating requires the existence of oxygen.In some embodiments, only organonitrogen reactive compounds or the compsn that comprises the organonitrogen reactive compounds are exposed to air and are enough to induced polymerization.In some embodiments, dissolved oxygen is enough in one or more in other components of compsn.In some embodiments; Restriction concentration of oxygen (but it not being got rid of from system) can be useful such as through using nitrogen purging (sweep) or purging (purge) for security (reducing the combustibility of volatile fluid), for reaction efficiency or the two.In order to stop the premature polymerization of oxygen under existing, can be physically or chemically separated portion (C) and component (E), up to just before the expected time of initiated polymerization and/or crosslinking reaction.For example, compsn can be at first as two kinds of independent formulations prepared from solutions, just initiated polymerization and/or crosslinked before they being combined.All the other components of compsn can be distributed between two kinds of solution by any way, as long as component (C) and component (E) do not contact with each other.For example, comprise component (A) and first solution (C) and comprise component (B) and second solution (E) is air-stable, but polymerization forms fine particle when in the presence of air, these solution being mixed.Alternatively, component (C) and (E) or the two, can be independent sealed or sent.For example, can solid form with component (C) and (E) one or both introduce silicon-ketone compositions, this stops their intimate admixture.The polymerization of compsn can be through following activation: (a) at the temperature heating combination of the softening temperature that is higher than solid components or sealing agent, or (b) allow component (C) and (E) blended solubilizing agent through introducing.Alternatively, component capable of being combined (C) and (E) and anaerobism be packaged in the single container, and can come initiated polymerization through introducing oxygen to compsn.
In some embodiments, optional organonitrogen reactive compounds is not the component of silicon-ketone composition.In such situation, radical polymerization can be through being exposed to air with organoborane compounds, through thermal activation, or causes via irradiation.In the situation of thermal activation, one or more components of compsn must be heated to the character decision of the temperature of initiated polymerization by the organoborane compounds that is elected to be component (C).For example, if organo-borane-organonitrogen mixture is elected to be component (C), the bound energy of mixture will determine compsn must be heated to disassociation of initiation mixture and polymeric temperature so.In some embodiments, component (C) can be heated before other components that are introduced into compsn.In some embodiments, component (C) and at least a other components were heated before any other component of introducing compsn.
Optional components (F), activeconstituents
Usually, optional components (F) comprises and can be added at least a personal care or the health care activeconstituents of silicon-ketone composition to be sealed by the elastomer particles original position.In some embodiments, can during the preparation silicone elastomer, component (F) be added to (prefill method) in the silicon-ketone composition, or can after forming silicone elastomer, add component (F) (back filling method).In some embodiments, the temperature at the threshold temperature that is lower than its thermal response or decomposition is incorporated into compsn with thermo-responsive activeconstituents.In some embodiments, the activeconstituents that suspends in the compsn can be, but do not require and be, with particle form.Sealing when being in particle form under the condition when activeconstituents, its particle size, distribution or shape are unrestricted.Through other components in the careful selection compsn, the characteristic of may command polymer beads is with the releasing mechanism of the expectation of permission activeconstituents.The instance of releasing mechanism comprises via heat, machinery and chemical stress extraction, dissolving, swelling, thawing, softens, degrades, grinds, pushes or break.
The amount of the component that exists in the silicon-ketone composition (F) can change; But in some embodiments based on the amount of the gross weight of component in the silicon-ketone composition (A)-(E), from about 0% to about 50% (by weight), alternatively from about 1% to about 25% (by weight), change from about 1% to about 10% (by weight) alternatively.
" personal care or the health care activeconstituents " that this paper uses refer to known in the art in personal care formulations as any compound of additive or the mixture of compound, it is made up and/or the purpose of aesthetic benefits and adding to provide in order to handle hair or skin usually; Known in the artly be used to provide any compound of pharmacy or medical benefit or the mixture of compound; Expection with diagnosis be provided, cure, alleviate, directly effect or of the pharmacological activity of treatment or preventing disease aspect or other with the structure that influences the mankind or other animal body or any compound of any function; With in the medicine manufacturing, can experience chemical transformation and form that can modification and in medicine, exists, expect regulation activity or any compound that acts on are provided.Therefore; " personal care and health care activeconstituents " includes but not limited to; Commonly used and by the U.S. healthy that define with government utility food and drug administration (United States Department of Health & Human Services Food and Drug Administration), be included in CFR; Title 21, the I chapters, activeconstituents or active pharmaceutical ingredient in 200-299 part and the 300-499 part.
Some representative example of personal care and health care activeconstituents include but not limited to medicine; VITAMINs; Albumen; Spices or essence; Plant milk extract; Mineral substance; Hormone; Local antimicrobials is such as the antibiotic activity composition; Be used to treat the anti-mycotic activity composition of the ringworm of the foot, jock itch or tinea and acne; The styptic activity composition; The reodorant activeconstituents; Remove wart agent activeconstituents; Corn and callosity remover activeconstituents; Be used to treat the delousing activeconstituents of head louse, crab louse (crab lice) and body louse; Be used for control head scurf, seborrheic dermatitis or psoriatic activeconstituents; With sunburn prevention and therapeutical agent.
In some embodiments, the activeconstituents that is suitable for component (F) comprise fat or oil-soluble vitamine and water-soluble vitamins both.The oil-soluble vitamine that can be used as component (F) includes but not limited to, the ester of the C2-C18 ester of retinol1, Vogan-Neu, Vogan-Neu, vitamin E, Viteolin, vitamin E, and composition thereof.Vogan-Neu comprises trans Vogan-Neu, 1,3-cis retinol, 11-cis retinol, 9-cis retinol and 3,4-two dehydroretinols.It should be noted that, Vogan-Neu be by U.S.'s makeup and fragrance association (The Cosmetic, Toiletry, and Fragrance Association, CTFA), the international nomenclature cosmetic composition title (INCI) of the specified vitamin A of Washington DC.Being included in other suitable vitamins of this paper and the INCI title of the VITAMINs of being thought is retinyl acetate, Vogan-Neu cetylate, Vogan-Neu propionic ester, alpha-tocopherol, Tocophersolan, VITAMIN E ACETATE, Vitamin E linoleate, tocopheryl nicotinate and tocopherol succinate.
The water-soluble vitamins that can be used as component (F) includes but not limited to, vitamins C, VITMAIN B1, Wei ShengsuB2, Y factor, cobalamin, nicotinic acid, folic acid, vitamin H and pantothenic acid.The INCI title that is included in other the suitable water-soluble vitamins of this paper and the VITAMINs of being thought is Vitamin C dipalmitate, xitix methyl-monosilane alcohol pectate, Quicifal and ascorbyl stearate.
Some instances that are suitable as the commercially available product of component (F) are: and vitamins C, and the two all is Fluka Chemie AG, Buchs, the product of Switzerland; COVI-OXT-50, Henkel Corporation, La Grange, the vitamin E product of Illinois; COVI-OXT-70, Henkel Corporation, La Grange, the another kind of vitamin E product of Illinois; And vitamin E, Roche Vitamins & Fine Chemicals, Nutley, the product of New Jersey.
In some embodiments, personal care or the health care activeconstituents as component (F) can be water-soluble or the oil soluble active pharmaceutical ingredient.The representative example of the more spendable water-soluble active pharmaceutical cpd that is fit to is a HYDROCORTISONE INJECTIONS; KP; Timolol; Pilocarpine; Adriamycin; Ametycin; Morphine; Hydromorphone; Odizem; Theophylline; Dx; Daunorubicin; Heparin; Penicillin G; Gepcillin; Cephalothin; Cefoxitin; Cefotaxime; 5 FU 5 fluorouracil; Cytosine arabinoside; The 6-azauridine; The 6-Tioguanine; Vinealeucoblastine(VLB); Vincristine(VCR); BLEOMYCIN SULPHATE; Aurothioglucose; Suramine and mebendazole.
The representative example that can be used as some oil soluble active pharmaceutical ingredients that are fit to of component (F) is clonidine, Scopolamine, Proprasylyte, Thinz-Span, ouabain, coromegine, haloperidol, Isosorbide, pannonit, Ibuprofen BP/EP, ubiquinone, INDOMETHACIN BP99, prostaglandin(PG), NAPROXEN USP /BP2000, salbutamol, guanabenz, Trate, pheniramine, metrifonate and steroid.
For the purposes of the present invention, think that being included in this paper is anti-acne agents such as Lucidol and tretinoin as active pharmaceutical ingredient; Antiseptic-germicide is such as chlorhexidine gluconate; Anti-mycotic agent is such as miconazole nitrate; Anti-inflammatory agent; Corticosteroid medication; The on-steroidal anti-inflammatory agent is such as diclofenac; Anti-psoriatic agent is such as clobetasol propionate; Narcotic is such as lignocaine; Pruritus; Anti-dermatitis agent; With the agent that is commonly referred to be barrier membranes.
In some embodiments, component (F) can also be an albumen, such as enzyme.Enzyme includes but not limited to: be purchased type, modified version, recombinant type, wild-type, the non-existent variant of nature, and composition thereof.For example, suitable enzyme comprises lytic enzyme, at, oxydase, transferring enzyme, reductase enzyme, hemicellulase, esterase, isomerase, polygalacturonase, Sumylact L, px, laccase, catalase and composition thereof.Lytic enzyme includes but not limited to: proteolytic enzyme (bacterium, fungi, tart, neutral or alkalescence), glycase (α or β), lipase, mannase, cellulase, collagenase and composition thereof.
In some embodiments, component (F) can be an opalizer.Opalizer can be selected from any opalizer that protection skin known in the art avoids being exposed to the harmful effect under the sunshine.Opalizer can be organic cpds, mineral compound or its mixture.Therefore, can comprise as the representational limiting examples of opalizer: benzaminic acid, cinoxate, diethylolamine Methoxycinnamate, digalloyl trioleate, dioxybenzone, 4-[two (hydroxypropyl)] subcutin, glyceryl aminobenzoate, homosalate, the lawsone that contains otan, Sunburn preventive No. 2, Suvor 3039, octyl methoxycinnamate, octyl salicylate, oxybenzone, the different monooctyl ester of p-(dimethylamino)-benzoic acid, Phenylbenzimidazolesulfonic acid, red petrolatum, sulisobenzone, titanium oxide and triethanolamine salicylate.
Organic sunscreen compounds is selected from the organic cpds of absorbing ultraviolet light (UV) usually.Some instances of UV light-absorbing compound have acetaminosalol; Wallantoin PABA; Benzal phthalide; UVNUL MS-40; UVNUL MS-40 1-12; The 3-benzylidene camphor; Benzylidene camphor hydrolytic collagen sulphonamide; Benzylidene camphor sulfonic acid; Benzyl salicylate; Prosolal S 9; VS 550; PAROSOL 1789; Butyl PABA; Cerium oxide/silicon dioxide; The cerium oxide/silicon dioxide talcum; Cinoxate; The DEA-Methoxycinnamate; The dibenzoxazine naphthalene; Di-t-butyl hydroxyl benzylidene camphor; Two galloyl trioleates; Di-isopropyl tolyl acrylic acid ester; Dimethyl PABA ethyl cetearyl Dimethyl Ammonium tosylate; Uvasorb HEB; Diphenylmethyl ester group acetoxyl group aphthopyrans; The equal phenylbenzene disulfonic acid of two ethylphenyl triamino triazines disodium; The equal phenylbenzene disulfonic acid of distyryl biphenyl base triamino triazine disodium; Distyryl biphenyl base disulfonic acid disodium; Drometrizole; The drometrizole trisiloxanes; Ethyl dihydroxypropyl PABA; The di-isopropyl ETHYL CINNAMATE; The methoxy cinnamic acid ethyl ester; Ethyl PABA; The urocanic acid ethyl ester; The Viosorb 910 FLA; Glyceryl octanoate dimethoxy-cinnamic acid ester; Glyceryl PABA; Glycol salicylate; Homosalate; Neo Heliopan E1000; Whitfield's ointment sec.-propyl benzyl ester; Isopropyl diphenyl formyl radical methane; The methoxy cinnamic acid isopropyl ester; Sunburn preventive No. 2; Menthyl salicylate; 4 methyl benzylidene camphor; Suvor 3039; Octrizole; Octyldimethyl PABA; Octyl methoxycinnamate; Octyl salicylate; UVINUL T-150; PABA; PEG-25PABA; The amyl group dimethyl PABA; Phenylbenzimidazolesulfonic acid; Polyacrylamide amino methyl benzylidene camphor; Methoxy cinnamic acid potassium; Phenylbenzimidazolesulfonic acid potassium; Red petrolatum; Phenylbenzimidazolesulfonic acid sodium; Urocanic acid sodium; TEA-Phenylbenzimidazolesulfonic acid salt; The TEA-salicylate; The Terephthalidene Dicamphor Sulfonic Acid; Titanium oxide; Three PABA panthenols; Urocanic acid and VA/ crotonate/methacryloxy UVNUL MS-40 multipolymer.
Alternatively; Opalizer is based on the organic cpds of laurate; Or alternatively; Opalizer is an octyl methoxycinnamate, such as
MC 80, the ester of a kind of p-methoxycinnamic acid and 2-Ethylhexyl Alcohol.
In some embodiments, component (F) can be spices or essence.Essence can be any essence or the spices activeconstituents that is generally used for essence industry.These compsns belong to number of chemical article classification usually, between the essential oil of the compound of alcohols, aldehydes, ketone, ester class, ethers, acetate, nitrite, terpene hydrocarbon, heterocyclic nitrogen containing or sulphur and natural source or synthetic source, change.At the standard textbook reference, Perfume and Flavour Chemicals for example, 1969, S.Arctander, Montclair has described many in these perfume ingredients in detail among the New Jersey.
Spices can be exemplified as, but is not limited to: aromatic ketone (perfume ketone) and aromatic aldehyde (perfume aldehyde).The example of aromatic ketone is the withered oxime of cloth, isojasmone, methyl-betanaphthyl ketone, Moschus indolone, tonalide/Moschus, α-trans-Damascenone, dorinone, δ-trans-Damascenone, different trans-Damascenone, damascenone, big horse rose ketone (Damarose), two hydrogen methyl jasmonate, piperitone, Karvon, camphor, fenchone, α-Zi Luolantong, alpha, beta-lonone, so-called cetone gamma, fleuramone, two hydrogen jasmone, cis-jasmone, ambrotone, methyl-cypress thiazolinyl-ketone or methyl-cedrone, methyl phenyl ketone, methyl-acetophenone, to methoxyl group-methyl phenyl ketone, methyl-β-naphthalenone, benzyl acetone, UVNUL MS-40, to hydroxyl-phenyl-butanone, apione (Celery Ketone) or apione (Livescone), 6-sec.-propyl decahydro-2-naphthalenone, dimethyl--octene ketone, bright piperitone (Freskomenthe), 4-(1-vinyl ethyl ether base)-3; 3; 5; 5-tetramethyl-ring hexanone, methyl-heptenone, 2-(2-(4-methyl-3-tetrahydrobenzene-1-yl) propyl group)-ketopentamethylene, 1-are (to menthene-6 (2)-yl)-1-acetone, 4-(4-hydroxy 3-methoxybenzene base)-2-butanone, 2-ethanoyl-3; 3-dimethyl--norbornane, 6; 7-dihydro-1; 1; 2; 3; 3-pentamethyl--4 (5H)-indolone, 4-damascol, piperonylacetone (Dulcinyl) or piperonylacetone (Cassione), 2-hexyl methyl aceto acetate (Gelsone), allyl ionone (Hexalon), ambrotone E, methyl ring lemon ketone (Methyl Cyclocitrone), methyl lavandula angustifolia ketone, 4-tert-pentyl pimelinketone (Orivon), to the tertiary butyl-pimelinketone, the 2-tertiary butyl six phenolic esters (Verdone), 2-amyl group pentamethylene (Delphone), muskone, new methylene acetone, medicine ketone musk, all roads ketone, 2,4,4; 7-tetramethyl--oct-6-ene-3-ketone and 3; 4,5,6-tetrahydropseudoionone (Tetrameran).
More preferably; Aromatic ketone is selected from according to its odor characteristics: α-trans-Damascenone, δ-trans-Damascenone, different trans-Damascenone, Karvon, cetone gamma, ambrotone, 2; 4; 4,7-tetramethyl--oct-6-ene-3-ketone, benzyl acetone, dorinone, trans-Damascenone, jessamona, methyl-cedrone and composition thereof.
Preferably, aromatic aldehyde is selected from according to its odor characteristics: A Daoke aldehyde, aubepine, cyclamen aldehyde (cymal), vanillal, cyanine aldehyde, helional, piperonylaldehyde, laurine, the unusual amylene of ethanoyl dimerization (koavone), lauryl aldehyde, LYRAL, methyl nonyl acetaldehyde, fragrant acetaldehyde (P.T.bucinal), phenyl acetaldehyde, undecylene aldehyde, Vanillin, 2,6; 10-trimethylammonium-9-undecylene aldehyde, 3-laurylene-1-aldehyde, α-n-pentyl phenylacrolein, 4-methoxybenzyl aldehyde, benzyl aldehyde, 3-(4-tert-butyl-phenyl)-propionic aldehyde, 2-methyl-3-(p-methoxyphenyl) propionic aldehyde, 2-methyl-4-(2,6,6-trimethylammonium-2 (1)-tetrahydrobenzene-1-yl) butyraldehyde, 3-phenyl-2-propenal, suitable/anti--3; 7-dimethyl--2,6-octadiene-1-aldehyde, 3,7-dimethyl--6-octene-1-aldehyde, [(3; 7-dimethyl--6-octenyl) oxygen base] acetaldehyde, 4-sec.-propyl benzyl aldehyde, 1,2,3; 4,5,6; 7,8-octahydro-8,8-dimethyl--2-naphthaldehyde, 2; 4-dimethyl--3-tetrahydrobenzene-1-formaldehyde, 2-methyl-3-(isopropyl phenyl) propionic aldehyde, 1-capraldehyde, capraldehyde, 2,6-dimethyl--5-heptenal, 4-(three ring [5.2.1.0 (2,6)]-Ya decyls-8)-butyraldehyde, octahydro-4; 7-methylene radical-1H-indenes formaldehyde, 3-oxyethyl group-4-hydroxyl benzyl aldehyde, to ethyl-α, alpha-alpha-dimethyl Qing Huarouguiquan, Alpha-Methyl-3,4-(methylene radical dioxy base)-Qing Huarouguiquan, 3; 4-methylene radical dioxy base benzyl aldehyde, α-n-hexyl phenylacrolein, a cymene-7-formaldehyde, Alpha-Methyl phenyl acetaldehyde, 7-hydroxyl-3,7-dimethyl-octanal, undecylene aldehyde, 2,4; 6-trimethylammonium-3-tetrahydrobenzene-1-formaldehyde, 4-(3) (4-methyl-3-pentenyl)-3-tetrahydrobenzene-formaldehyde, 1-NSC 46128,2,4-triplal, 4-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-formaldehyde, 7-methoxyl group-3,7-dimethyl-octa-1-aldehyde, the 2-methyl undecyl aldehyde, 2-methyl capraldehyde, 1-aldehyde C-9,1-octanal, 2; 6,10-trimethylammonium-5,9-undecadienal, 2-methyl-3-(the 4-tertiary butyl) propionic aldehyde, dihydro cinnamon aldehyde, 1-methyl-4-(4-methyl-3-pentenyl)-3-tetrahydrobenzene-1-formaldehyde, 5 or 6 methoxyl group 10-six hydrogen-4; 7-methylene radical indane-1 or 2-formaldehyde (5 or 6methoxyl, 0 hexahydro-4,7-methanoindan-1 or 2-carboxaldehyde), 3,7-dimethyl-octa-1-aldehyde, the 1-undecyl aldehyde, 10-hendecene-1-aldehyde, 4-hydroxyl-3-methoxybenzyl aldehyde, 1-methyl-3-(4-methyl amyl)-3-tetrahydrobenzene formaldehyde, 7-hydroxyl-3; 7-dimethyl--octanal, trans-4-decenal, 2,6-violet leaf aldehyde, p-methylphenyl acetaldehyde, 4-aminomethyl phenyl acetaldehyde, 2-methyl-4-(2,6; 6-trimethylammonium-1-tetrahydrobenzene-1-yl)-and crotonic aldehyde, o-methoxy cinnamic aldehyde, 3,5,6-trimethylammonium-3-tetrahydrobenzene formaldehyde, 3; 7-dimethyl--2-methylene radical-6-octenal, phenoxy acetaldehyde, 5,9-dimethyl--4,8-decadienal, tree peony aldehyde (6; 10-dimethyl--3-oxa--5,9-11 carbon diene-1-aldehyde), six hydrogen-4,7-methylene radical indane-1-formaldehyde, 2-methyl aldehyde C-9, Alpha-Methyl-4-(1-methylethyl) phenylacetic aldehyde, 6; Firpene-2-propionic aldehyde falls in 6-dimethyl--2-, to methylenedioxy phenoxy ethylhexanal, 2-methyl-3-phenyl-2-propylene-1-aldehyde, 3; 5,5-trimethylammonium hexanal, six hydrogen-8,8-dimethyl--2-naphthaldehyde, 3-propyl group-dicyclo [2.2.1]-heptan-5-alkene-2-formaldehyde, 9-decenal, 3-methyl-5-phenyl-1-valeral, methyl nonyl acetaldehyde, hexanal, trans-the 2-hexenoic aldehyde, 1-p-menthene-q-formaldehyde (1-p-menthene-q-carboxaldehyde) and composition thereof.
Preferred aldehyde is selected from according to its odor characteristics: 1-capraldehyde, benzyl aldehyde, cyanine aldehyde, 2; 4-dimethyl--3-tetrahydrobenzene-1-formaldehyde, cis/trans-3; 7-dimethyl--2,6-octadiene-1-aldehyde, piperonylaldehyde, 2,4; 6-trimethylammonium-3-tetrahydrobenzene-1-formaldehyde, 2,6-violet leaf aldehyde, α-n-pentyl phenylacrolein, α-n-hexyl phenylacrolein, fragrant acetaldehyde, LYRAL, cyclamen aldehyde, methyl nonyl acetaldehyde, hexanal, trans-2-hexenoic aldehyde and composition thereof.
In the above-mentioned tabulation of perfume ingredient, some are trade(brand)names that those skilled in the art know usually, and also comprise isomer.Such isomer also is suitable for the present invention.
In some embodiments, component (F) can be one or more plant milk extracts.The instance of these components is following: the angelica keiskei koidzumi extract; The avocado extract; The Flower of Largeleaf Hydrangea extract; The hollyhock extract; The arnica extract; Aloe extract; Fructus Pruni extract; The almond extract; Semen Ginkgo extrac; Fructus Foeniculi extract; Turmeric [turmeric] extract (turmeric [Curcuma] extract); Oolong tea extract; The rose hip extract; The Echinacea extract; The scutellariae,radix extract; The Berberis Amurensis Rupr extract; The coptis japonica Makino extract; Fructus Hordei Vulgaris extract; The Radix Hyperici Monogyni (Herba Hyperici Monogyni) extract; White nettle extract; The watercress extract; The orange extract; The dehydration seawater; Seaweed Extract; Elastin hydrolysis; The hydrolyzed wheat powder; Hydrolyzed-silk; Flos Chrysanthemi extract; Radix Dauci Sativae extract; Artemisiae argyi extract; Radix Glycyrrhizae extract; The Flos Hibisci Mutabilis tea extract; Fire sour jujube berry extract; Fructus actinidiae chinensis extract; The Peruvian bark extract; Fructus Cucumidis sativi extract; Guanosine (guanocine); Fructus Gardeniae extract; The Indocalamus leaf extract; The radix sophorae extract; The walnut extract; Grapefruit extract; Radix Clematidis extract; Chlorella extract; Mulberry extract; Radix Gentianae extract; Black tea extract; Yeast extract; The burdock extract; The rice bran fermented product extract; Big rice embryo oil; Radix Arnebiae extract; Collagen protein; Pericarpium Citri tangerinae extract; Fructus Gardeniae extract; The Radix Asari extract; Radix bupleuri family extract; Sage extract; The Saponaria officinalis extract; Bamboo extract; The haw extract; Pericarpium Zanthoxyli fruit (Zanthoxylum fruit) extract; Shitake Mushroom P.E; The Radix Rehmanniae extract; Radix Arnebiae extract; Folium perillae extract; The linden extract; The palmate meadowsweet extract; Radix Paeoniae Alba extract; The Rhizoma Acori Graminei extract; The white birch extract; The horse hair extract; The ivy extract; Fructus Crataegi extract; European elder (Sambucus nigra) extract; Achillea millefolium (Achillea millefolium) extract; Peppermint (Mentha piperita) extract; Sage extract; The high mallow extract; The Ligusticum wallichii root extract; Japan's green gentian extract; Soybean extraction; Fructus Jujubae extract; Thymi Serpylli Herba extract; Tea extract; Flos Caryophylli extract; Gramineae cogon extract; The mandarin orange peel extract; The Angelica acutiloba root extract; The mary bush extract; Semen Persicae extract; The bitter taste Pericarpium Citri junoris extract; Herba Houttuyniae extract; Fructus Lycopersici esculenti extract; Natto extract; Radix Ginseng extract; Green tea extract (camellia); Bulbus Allii extract; The wild rose extract; Rose of Sharon extract; The tuber of dwarf lilyturf root tuber extract; The lotus extract; Parsley extract; Honey; The witch hazel extract; The wall pellitory extract; Herba Rabdosiae Lophanthoidis extract; The Hydagen B extract; The loquat extract; The coltsfoot extract; Butterbur extract (butterbur extract); Poria extract; The Ruscus extract; Fructus Vitis viniferae extract; Propolis extract; Fructus Luffae extract; Flos Carthami extract; Folium Menthae extract; The lime tree extract; Radix Paeoniae Alba extract; Flos lupuli (Flos Humuli Lupuli) extract; Pine extract; The horse-chestnut extract; Water plantain (Mizu-bashou) extract; The Seed of Chinese Soapberry peel extract; The Herba melissae axillaris extract; The peach extract; The Minor centaury extract; Eucalyptus extracts; Herba Saxifragae extract; The citron extract; Semen Coicis extract; Biennial wormwood extract; Herba Lysimachiae foenumgraeci extract; Fructus Mali pumilae extract; The romaine lettuce extract; Citron extract; China's Radix Astragali extract; Rose extract; Rosemary extract; Flores anthemidis extract and royal jelly extract.
In some embodiments, component (F) is personal care or the health care activeconstituents that is selected from VITAMINs, opalizer, plant milk extract, spices or essence, part drug's actives, albumen (including but not limited to enzyme), antiperspirant, reodorant, moistening agent, anti-mycotic agent and antiseptic-germicide.
Optional components (G), emulsifying agent
Usually, optional components (G) comprises and can be added into silicon-ketone composition with at least a emulsifying agent of emulsifying elastomer particulate." emulsifying agent " that this paper uses is meant any compound or the material that can form emulsion.Emulsion can be oil/water miscible liquid, water/fat liquor, heterogeneous or triple emulsion.Emulsifying agent is optional from any surface active cpd or polymkeric substance that can stable emulsion.Usually, such surface active cpd or polymkeric substance come stable emulsion through stoping the dispersed particles coalescence.The surface active cpd that can be used as emulsifying agent in the method can be the combination of tensio-active agent or tensio-active agent.In principle, the tensio-active agent of use can be any tensio-active agent that becomes known for the emulsification silicone, and can be cationic, anionic, non-ionic type and/or amphoteric.
The instance of cationic surfactant includes but not limited to quaternary ammonium hydroxide, for example the quaternary ammonium hydroxide of corresponding salt, aliphatic amide and the fatty acid amide of octyl group trimethylammonium hydroxide, dodecyl trimethylammonium hydroxide, cetyltrimethylammonium hydroxide, octyldimethyl benzylic hydrogens ammonium oxide, decyl dimethyl benzyl volatile caustic, two dodecyl dimethyl volatile caustic, two octadecyl dimethyl hydrogen ammonium oxide, butter trimethylammonium hydroxide and cocounut oil trimethylammonium hydroxide and these materials and their verivate, alkaline pyridine compounds and benzimidazoline and gather (ethoxylated/propoxylated) amine.
The instance of aniorfic surfactant includes but not limited to for example dodecyl sulfate, polymkeric substance for example hexyl benzene sulfonic acid, octyl group Phenylsulfonic acid, decyl Phenylsulfonic acid, Witco 1298 Soft Acid, hexadecyl Phenylsulfonic acid and myristyl Phenylsulfonic acid of propenoate/C10-30 alkyl acrylate cross-linked polymer, alkyl benzene sulphonate(ABS) and salt for example of alkyl-sulphate; The sulfuric ester of monoalkyl Soxylat A 25-7; Alkyl naphthyl sulfonic acid; The sulfonated glyceryl ester of basic metal sulfosuccinate (alkali metal sulfoccinate), lipid acid is condensation product, octahydro anthracene sulfonic acid sodium, alkali metal alkyl sulfate, ester vitriol and the alkylaryl sulfonate of sulfonated products, sulfonated aromatic hydrocarbon, naphthene sulfonic acid and the formaldehyde of salt, sulfamic acid amides, the fatty acid nitrile of sulfonation monoglyceride, the sulfonation monovalence alcohol ester of cocinic acid for example.The alkali metal soap, alkylaryl sulphonate that aniorfic surfactant comprises higher fatty acid be X 2073, long-chain fat alcohol sulfate, olefin sulphates and alkene sulfonate, Sulfated monoglyceride, Sulfated ester, sulfonated ethoxylated alcohol, sulfosuccinate, alkane sulfonate, SULPHOSUCCINIC ACID ESTER, alkyl isethionate, alkyl tauride and alkyl sarcosine salt for example.
The instance of non-ionics includes but not limited to, ethylene oxide and long chain aliphatic alcohol or lipid acid is condensation product, glyceryl ester, sucrose, Sorbitol Powder, fatty acid alkyl amide, sucrose ester, fluorine surfactant, fatty amine oxide, the polyoxyalkylene alkyl for example Z 150PH (PVA) and the polyvinyl methyl ether of polyethylene glycol long chain alkyl oxide, polyoxyalkylene sorbitanic ether, polyoxyalkylene alcoxylates ester, polyoxyalkylene alkyl phenol ether, terepthaloyl moietie propylene glycol copolymers and alkyl polysaccharide, polymeric surfactant for example of condenses, ethene and the propylene oxide of condenses, ethylene oxide and amine or the acid amides of C12-C16 alcohol for example.In certain embodiments, tensio-active agent is the mixture of T 46155 Fatty Alcohol(C12-C14 and C12-C18) or T 46155 Fatty Alcohol(C12-C14 and C12-C18).In other embodiments, tensio-active agent is the water dispersion of T 46155 Fatty Alcohol(C12-C14 and C12-C18) or T 46155 fatty alcohol mixture.
Examples of amphoteric surfactants comprises AMONYL 380LC, cocamidopropyl propyl amide Hydroxysulfate, coco betaine, coconut oleoyl amine sodium acetate, coco dimethyl trimethyl-glycine, N-cocoyl-3-propalanine and tetrahydroglyoxaline carboxylic compound.
Tensio-active agent can be moisture, non-water, and/or with dilution or undiluted form.Therefore, the desired characteristic of the tensio-active agent of selection, its moisture/non-aqueous matter, its dilution/undiluted form and emulsion will determine whether to add other water and form emulsion.
In an alternative embodiment, emulsifying agent can be polymkeric substance or those materials of thinking " viscosifying agent " or " thickening material " in this area.Such polymeric emulsifiers includes but not limited to, Z 150PH, cellulose polymer compound or XG 550.Z 150PH comprises the Z 150PH of hydrolysis, such as the Z 150PH of 80-95% hydrolysis.The thickening material that is fit to comes example through following: sodiun alginate, Sudan Gum-arabic, T 46155, guar gum, hydroxypropylguar gum, ethoxylation alcohols, and such as laureth-4 or PEG 400, by CMC 99.5, methylcellulose gum, methylhydroxypropylcellulose, hydroxypropylcellulose, the derivatived cellulose that gathers propyl group Natvosol example, starch with by the starch derivative of hydroxyethyl amylose starch and amylose starch example, Viscogum BE, by ionogen and carbohydrate such as fructose and glucose and carbohydrate derivative such as PEG-120 methyl glucoside dioleate or 2 kinds or more kinds of mixtures in these of sodium-chlor and ammonium chloride example.Usually; Thickening material is selected from the group of being made up of derivatived cellulose, carbohydrate derivative and ionogen; Or being selected from two kinds or more kinds of combinations in the above thickening material, this combination comes example by derivatived cellulose and any ionogen, starch derivative and any electrolytical combination.
Although many emulsifying agents are suitable as component (G), through selecting secondary alcohol ethoxyl compound such as Tergitol
TM15-s-3, Tergitol
TM15-s-40, poly ethyldiol modified siloxanes, poly ethyldiol modified trimethyl silicone hydride silicate, ethoxylated quaternary solution and palmityl trimethyl ammonium chloride solution have obtained good result.
Other optional components
Silicon-ketone composition also can comprise other component.Not restrictedly, the instance of so optional other component does not comprise tensio-active agent; Emulsifying agent; Dispersion agent; Polymerization stabilizer; Linking agent; Can be used for providing the combination of particulate after polymerization or crosslinked polymkeric substance, linking agent and catalyzer; Rheology modifier is such as viscosifying agent; Density properties-correcting agent; The Soluol XC 100 stablizer; Cured modified dose such as quinhydrones with by the amine that hindered; Radical initiator such as organo-peroxide and ozonide; Polymkeric substance; Thinner; Acid acceptor; Inhibitor; Thermo-stabilizer; Fire retardant; Scavenging agent; Silylating agent; Suds-stabilizing agent; Solvent; Thinner; Softening agent; Weighting agent and inorganic particle, pigment, dyestuff and siccative.
Can comprise according to compsn of the present invention and to be selected from those the multiple optional components that is known as the composition in individual and the health care preparation in this area.Illustrative, limiting examples comprise tensio-active agent, solvent, powder, tinting material, viscosifying agent, wax, stablizer, pH regulator agent and silicone.
Can be randomly add the viscosity of thickening material to provide convenience to the water of compsn.For example, 25 ℃ or when higher 500 to 25,000mm
2In the scope of/s, alternatively in the time of 25 ℃ 3,000 to 7,000mm
2Viscosity in the scope of/s normally is fit to.The thickening material that is fit to comes example through following: sodiun alginate; Sudan Gum-arabic; T 46155; Guar gum; Hydroxypropylguar gum; The ethoxylation alcohols is such as laureth-4 or PEG 400; By methylcellulose gum, methylhydroxypropylcellulose, hydroxypropylcellulose, gather the derivatived cellulose of propyl group Natvosol example; Starch and by the starch derivative of hydroxyethyl amylose starch and amylose starch example; Viscogum BE; Ionogen by sodium-chlor and ammonium chloride example; Carbohydrate such as fructose and glucose; With carbohydrate derivative such as PEG-120, methyl glucoside dioleate; Or two kinds or more kinds of mixture in these.Thickening material is selected from derivatived cellulose, carbohydrate derivative and ionogen alternatively, or is selected from two kinds or more kinds of combinations in the above thickening material, and this combination comes example by derivatived cellulose and any ionogen, starch derivative and any electrolytical combination.Thickening material can be in shampoo Compositions of the present invention to be enough to provide in the final shampoo Compositions from 500 to 25,000mm
2The amount of the viscosity of/s exists.Thickening material can be based on the gross weight of compsn from about 0.05 to 10wt%; Exist from about amount of 0.05 to 5wt% alternatively.Also can add viscosifying agent, such as polyacrylic ester cross-linked polymer, propenoate/C1030 alkyl acrylate cross-linked polymer, polyacrylamide derivative, ZX-I based on acrylate derivative.
Stablizer can be randomly uses at the aqueous phase of the present composition.The water stablizer that is fit to can comprise alone or in combination one or more ionogen, polyvalent alcohol, alcohols such as ethanol and hydro-colloid.Typical ionogen is muriate, borate, Citrate trianion and vitriol and chlorination hydroxyl aluminium and polyelectrolyte, especially mucinase and the hyaluronate sodium of an alkali metal salt and alkaline earth salt, especially sodium, potassium, calcium and magnesium.When stablizer is an ionogen or when comprising ionogen, its equal total compsn about 0.1 to 5wt%, more alternatively 0.5 to 3wt%.Hydro-colloid comprises that glue class such as XG 550 or neusilin and thickening material are such as CMC 99.5.Also can use polyvalent alcohol such as glycerine, glycols and Sorbitol Powder.Optional polyvalent alcohol is glycerine, Ucar 35, Sorbitol Powder and butyleneglycol.If use big weight polyalcohol, people not demand add ionogen.Yet, use the combination of ionogen, polyvalent alcohol and hydro-colloid to stablize water usually, for example sal epsom, butyleneglycol and XG 550.
Other optional components can comprise powder and pigment, especially when compositions contemplated according to the present invention is used for makeup.Powdery components of the present invention is defined as drying, the particulate matter of the particle size with 0.02-50 micron usually.Particulate matter can be coloured or colourless (for example white).The powder that is fit to includes but not limited to, bismuthyl chloride, metatitanic acid mica, aerosil, preparing spherical SiO 2 pearl, polymethylmethacrylate pearl, SP 1, pure aluminium silicate, starch octenyl succinic aluminium, wilkinite, kaolin, neusilin, silicon-dioxide, silylanizing silicon-dioxide, talcum, mica, titanium oxide, nylon, silk powder.But the above-mentioned powder of surface treatment is so that particulate character is hydrophobic.Powdery components also comprises multiple pigment dyestuff and mineral dye.The normally multiple aromatics type of pigment dyestuff, comprise azo, indigo-blue, tritane, anthraquinone and xanthin dyestuff, it is called as D&C and FD&C is blue, brown, green, orange, red, Huang etc.Mineral dye is made up of the insoluble metal-salt of the color additives that is called color lake or red stone of examining and determine usually.Coloured powdery agent such as carbon black, chromic oxide or red stone, ultramarine, manganese pyrophosphate, barba hispanica and titanium oxide, pearling agent; Usually conduct is used with the mixture of colored pigment or some organic dye; Usually the mixture of conduct and colored pigment uses and is usually used in cosmetic industry, can add compsn to.Usually, these tinting materials can exist with respect to from 0 to 20% the amount by weight of final composition weight.
Also can add the inorganic or organic filler of powdery, usually with from 0 to 40% amount by weight with respect to final composition weight.These powdered fillers can be selected from talcum; Mica; Kaolin; Zinc oxide or titanium oxide; Lime carbonate or magnesiumcarbonate; Silicon-dioxide; Spherical tio2; Glass or ceramic bead; Metallic soap derived from carboxylic acid with 8-22 carbon atom; Unexpansive synthetic polymer powder; Expansion powder and from the powder (it can be crosslinked or can not be crosslinked) of natural organic-compound such as cereal starch; Copolymer microsphere such as EXPANCEL (Nobel Industrie); Polytrap and silicone resin microballon (for example from Toshiba TOSPEARL).
Wax or wax appearance material can be the optional components of the present composition, and wherein such component has 35 ℃ to 120 ℃ melting range under atmospheric pressure usually.Wax in this type comprises synthetic wax, ceresin, paraffin, ceresine, beeswax, POLISHING WAX-103, crystallite, yolk, lanolin derivative, gama wax, theobroma oil, shellac wax, spermaceti, rice bran wax, kapok wax, sugar-cane wax, montanin wax, spermaceti, candleberry wax, soya wax or its mixture.Can mention animal wax, such as beeswax as in the wax of non-silicone fatty substance; Vegetable wax, such as POLISHING WAX-103, gama wax, mineral wax, for example paraffin or montanin wax or Microcrystalline Wax or ceresine; Synthetic wax comprises polyethylene wax and by the synthetic wax that obtains of Fischer-Tropsch.In silicone wax, can mention polymethyl siloxane alkyls, alcoxyl base class and/or ester class.
Optional components also can comprise siloxanes, alkyl methyl siloxanes, silicone resin and the silicone gum of silicone (comprise any described), organic functional.The alkyl methyl siloxanes that can be used for compsn of the present invention can have formula Me
3SiO [Me
2SiO]
y[MeRSiO]
ZSiMe
3, wherein R is the alkyl that contains 6-30 carbon atom, the Me represent methylidene, and the polymerization degree (DP) be y and z be 3-50.Can use in the compsn alkyl methyl siloxanes volatile matter and fluent meterial the two.Also can add the phenyl functional siloxane, such as Dow Corning
556 Fluid.
Silicone gum also can be the optional components of the present composition.Polydiorganosiloxane rubber is known in the art, and is available commercially.They surpass 1,000,000 centistoke (mm by having at 25 ℃ usually
2/ s), alternatively at 25 ℃ greater than 5,000,000 centistoke (mm
2/ s) the insoluble polydiorganosiloxane of viscosity is formed.These silicone gums are sold so that its processing as the compsn that is dispersed in the suitable solvent usually.Can comprise that also the hyperviscosity silicone [has from 25 ℃ of about 500 ten thousand centistoke (mm usually
2/ s) extremely at 25 ℃ of about 2,000 ten thousand centistoke (mm
2/ s) those of dynamic viscosity] as optional components.In some embodiments, the compsn of this type can be with form of suspension.
Silicone resin also can be the optional components in the present composition.The polymer siloxane that such resin is normally highly cross-linked.Crosslinkedly obtain through being incorporated into silane trifunctional and/or four functional silane and employed simple function and/or two functional silane monomers during manufacture.The required degree of crosslinking of silicone resin that obtains to be fit to will change according to the unitary characteristic of the silane monomer that is incorporated into during the silicone resin manufacturing.Usually, thus have enough levels trifunctional with four functional siloxane monomeric units, and to possess enough crosslinked levels be that any silicone of rigidity or dura mater can be thought and is suitable as silicone resin to dry up.The commercial obtainable silicone resin that is suitable for using is usually with the unhardened supplied in LV volatility or the non-volatile silicone fluid, and can its unhardened form rather than hardened arborescens structure be incorporated in the present composition.
Silicone methyl alcohol fluid also can be an optional components.These materials are described in WO 03/101, among the 412A2, and can be described as the siloxane fluid or the resin of substituted hydrocarbyl functional usually.
Water-soluble or water-dispersible silicone polyether compsn also can be an optional components.These are also referred to as the polyalkylene oxide silicone copolymer, silicone gathers (oxyalkylene) multipolymer, silicone diol copolymer or silicone surfactant.These can be straight chain rake or graft type material, ABA or ABn type, and wherein B is the siloxane polymer block, and A gathers (oxyalkylene) group.Gathering (oxyalkylene) group can be made up of T 46155, polyoxypropylene or blended polyoxyethylene/polyoxypropylene group.Other oxide compounds such as oxybutylene or phenylate also are possible.
Utilize silicone emulsifier, according to compsn of the present invention can o/w, o/o, o/s and s/o emulsion or the multi-phase emulsion of s/w, w/o, w/s and non-water use.Usually the silicone bag water emulsifier in such preparation is a non-ionic type, and is selected from polyoxyalkylene-substituted silicone (rake or ABn type), silicone alkylolamide, silicone ester class and silicone glycoside.The tensio-active agent based on silicone that is fit to is well known in the art, and for example has been described among US 4,122,029 (Gee etc.), US 5,387,417 (Rentsch) and US 5,811,487 (Schulz etc.), the JP 2001-294512.
When compsn according to the present invention is O/w emulsion, it will comprise the composition commonly used that is generally used for preparing emulsion, such as but be not limited to the non-ionics that is used to prepare the o/w emulsion known in this field.The instance of non-ionics comprises the polysiloxane surfactant of Voranol EP 2001, polyxyethylated alkylphenol, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate, polyxyethylated ester, polyoxyethylene sorbitol acid anhydride alkyl ester, polyoxyethylene glycol, W 166, glycol ether, ethoxylation Exxal 12 and polyoxyalkylene diols modification.
According to compsn of the present invention can also be aerocolloidal form associating propulsive gases, such as carbonic acid gas, nitrogen, Nitrous Oxide, volatile hydrocarbon such as butane, Trimethylmethane or propane and chlorination or fluoridize hydro carbons such as methyl chlorofluoride and dichloro tetrafluoro ethane or dimethylether.
The silicone particulate and the paste of hydrophilic modifying
According to a plurality of embodiments of the present invention, organopolysiloxane/hydrophilic organic copolymer particle is provided, comprises the silicone paste of such particulate and makes their method.In some embodiments, the silicone paste can prepare through comprising following method: (I) formation comprises following reaction mixture: component (A), at least a organopolysiloxane with at least two radical polymerizable groups of average per molecule; Component (B), at least a polymerisable organic comonomer of radical with at least one hydrophilic radical of per molecule; Component (C), at least a organo-borane radical initiator; Component (D) is with the immiscible at least a non-solvent of component (A); Component (E) randomly, at least a organonitrogen reactive compounds; Component (F) randomly is applicable at least a activeconstituents of personal care and health care products; Component (G) randomly, at least a emulsifying agent; (II) stirring reaction mixture in the presence of oxygen, and remain on from about 5 ℃ to about 95 ℃ temperature; Wherein stir and taking place during the combination of components, after combination of components, taking place or its combination; (III) allow generation polymerization and crosslinking reaction to have the water-insoluble silicone particulate of hydrophilic functional degree up to formation.But can microparticulate be formed the paste that has by fluid swollen silicone particulate at least a absorption fluids.In some embodiments, the swelling particle is a spheric basically.The silicone paste also can comprise at least a activeconstituents that is incorporated in the elastomer particles, and in some embodiments, forms compsn in room temperature and combine thermo-responsive activeconstituents to allow original position.The silicone paste of the method that provides is stable, and can have the viscosity of wide region, thereby makes them especially can be used as the basal component that is used for personal care (such as makeup) and health care products.Such paste characterizes with sensorial characteristics, thixotropy and the shear-thinning with pleasant usually.In some embodiments, the silicone paste composition comprises from about 5% elastomerics to about 50% (by weight); Alternatively, from about 10% elastomerics to about 30% (by weight).In some embodiments, the silicone paste composition has 25Pas at least, 40Pas at least alternatively, the viscosity of 100Pas at least alternatively.In some embodiments, paste has the viscosity from about 25Pas to about 100Pas.In some embodiments, paste has the viscosity from about 25Pas to about 40Pas.In some embodiments, paste has the viscosity from about 40Pas to about 100Pas.In some embodiments, paste has the viscosity greater than 100Pas.
In some embodiments, the silicone paste composition has mean diameter for from about 0.1 μ m to the swelling of the spheric basically silicone elastomer particulate of about 500 μ m.
In some embodiments, prolonged agitation component is up to forming compsn.In some embodiments, only stir, and stop then with initiation reaction.
In some embodiments, stir component and in the presence of oxygen, carry out, and maintain the temperature at from about 5 ℃ to about 95 ℃.Therefore, temperature can be from about 5 ℃ to about 10 ℃, from about 10 ℃ to about 15 ℃, from about 15 ℃ to about 20 ℃, from about 20 ℃ to about 25 ℃, from about 25 ℃ to about 30 ℃, from about 30 ℃ to about 35 ℃, from about 35 ℃ to about 40 ℃, from about 40 ℃ to about 45 ℃, from about 45 ℃ to about 50 ℃, from about 50 ℃ to about 55 ℃, from about 55 ℃ to about 60 ℃, from about 60 ℃ to about 65 ℃, from about 65 ℃ to about 70 ℃, from about 70 ℃ to about 75 ℃, from about 75 ℃ to about 80 ℃, from about 80 ℃ to about 85 ℃, from about 85 ℃ to about 90 ℃ and from about 90 ℃ to about 95 ℃.In some embodiments, stir and in the presence of oxygen, carry out, and maintain the temperature at from about 10 ℃ to about 35 ℃.Therefore, temperature can be 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃ and 35 ℃.
In some embodiments; The method of describing is an emulsion polymerisation process; Wherein will comprise being dispersed in mutually in the external phase that comprises component (D) of component (A), (B) and (C); And wherein form O/w emulsion when shearing, add component (E) compound (such as acid, isocyanic ester and epoxide) this moment, the deposition of insoluble polymer particulate takes place when applying.
In some embodiments; The method of describing is an emulsion polymerisation process; Wherein will comprise being dispersed in mutually in the external phase that comprises component (D) of component (A), (B) and (C), and wherein form O/w emulsion when applying when shearing, acidifying this moment causes the deposition of insoluble polymer particulate.
But absorption fluids
According to a plurality of embodiments of the present invention, the silicone elastomer that is formed by radical polymerization and crosslinking reaction is insoluble in component (D), but in being dispersed in some fluid the time, elastomerics absorbs this fluid and forms the swelling particle.Therefore, " but absorption fluids " means and is meant a kind of fluid that can be absorbed by silicone elastomer of the present invention.In some embodiments, but absorption fluids also can be used as elastomeric solvent.In some embodiments, but absorption fluids can with the water immiscible.
In some embodiments, but the absorption fluids that is fit to can be selected from silicone; Organic cpds; With " ecological close friend's " solvent, such as ion type liquid and supercutical fluid; And composition thereof.
But the instance that is used for the silicone that is fit to of absorption fluids includes but not limited to low molecular weight linear or ring-type volatile silicone; Non-volatile alkyl or aryl silicone; With low molecular weight linear or the functional silicone of ring-type.Silicone can miscible fluid can be single mixture of planting silicone or silicone.In some embodiments, but absorption fluids is to have (CH3)
XSiO
(4-x)/2The lower molecular weight volatility methyl silicone (VMS) of averaged unit formula, wherein x has from 2 to 3 MV.Representative Volume Element in such VMS compound is (CH
3)
3SiO
1/2Unit and (CH
3)
2SiO
2/2The unit, and additionally can have CH
3SiO
3/2Unit and/or SiO
4/2The unit, this causes forming side chain, straight chain or ring-type volatility methyl silicone.Straight chain VMS has formula (CH
3)
3SiO{ (CH
3)
2SiO}
ySi (CH
3)
3, wherein y is 0 to 5.Ring-type VMS has formula { (CH
3)
2SiO}
z, wherein z is 3 to 6.Usually these volatility methyl silicones have less than about 250 ℃ boiling point with from about 0.65 to 5.0 centistoke (mm
2/ s) viscosity.
In some embodiments; The silicone that is fit to includes but not limited to; Straight chain volatility methyl silicone is such as SWS-F 221, octamethyltrisiloxane, decamethyl tetrasiloxane, ten dimethyl-, five siloxanes, tetradecamethylhexasiloxane and ten hexamethyl, seven siloxanes; Ring-type volatility methyl silicone is such as hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane and ten diformazan basic rings, six siloxanes; With side chain volatility methyl silicone, such as seven methyl-3-{ (trimethyl silyl) oxygen base } trisiloxanes, hexamethyl-3,3, two { (trimethyl silyl) oxygen base } trisiloxanes and pentamethyl-{ (trimethyl silyl) oxygen basic ring trisiloxanes.
In some embodiments, non-volatile alkyl or aryl silicone includes but not limited to that straight chain gathers the alkyl or aryl silicone, such as formula R
4 3SiO (R
4 2SiO)
mSiR
4 3Compound; Gather the alkyl or aryl silicone with ring-type, such as formula (R
4 2SiO)
nCompound; R wherein
4The alkyl or the aryl that are 1 to 6 carbon atom be such as phenyl, and m has 0 to 80, preferably 0 to 20 value, and n has 0 to 9,4 to 6 value preferably.These silicone have usually at about 1 to 100 centistoke (mm
2Viscosity in/s) the scope.The non-volatile silicone of other representative lower molecular weights has R
5 3SiO (R
5R
6SiO)
pSiR
5 3Overall structure, wherein p has be provided at about 100 to 10,000 centistoke (mm for polymkeric substance
2The value of the viscosity in/sec) the scope, and R
5And R
6The alkyl or the aryl that are 1 to 30 carbon atom are such as phenyl.Usually, the value of p is about 60 to 600.Non-volatile ZGK 5 can be by following example, but is not limited to, and YSR 3286, gathers di-ethyl siloxane, polymethy ethylsiloxane, PSI and gathers diphenyl siloxane.
In some embodiments, the functional silicone of lower molecular weight can be by following representative: siloxane fluid, methyl ester functional siloxane fluid, perfluor functional siloxane fluid and the silanol functional siloxane of the siloxane fluid of the siloxane fluid of the siloxane fluid of the siloxane fluid of acrylic amide functional siloxane fluid, acrylate-functional, the siloxane fluid of amide functional, amino-functional, methyl alcohol functional siloxane fluid, carboxyl-functional, the siloxane fluid of chlorine alkyl functional, epoxy functionalized siloxane fluid, functionalized with glycols, ketal functional siloxane fluid, Mercaptofunctional.
In some embodiments, but absorption fluids is optional from organic cpds.Instance includes but not limited to, aromatic hydrocarbon; Aliphatic hydrocarbon; Alcohols; Aldehydes; Ketone; Amine; The ester class; Ethers; Glycols; Glycol ethers; Alkyl halide; Or aromatic halide.Organicly can further be exemplified as alcohols by miscible fluid, such as methyl alcohol, ethanol, 1-propyl alcohol, hexalin, benzylalcohol, sec-n-octyl alcohol, terepthaloyl moietie, Ucar 35 and glycerine; Aliphatic hydrocarbon is such as pentane, hexanaphthene, heptane, VM&P solvent and mineral turpentine; Alkyl halide is such as chloroform, tetracol phenixin, tetrachloroethylene, monochloroethane and chlorobenzene; Amine is such as Isopropylamine, hexahydroaniline, thanomin and diethylolamine; Aromatic hydrocarbon is such as benzene, toluene, ethylbenzene and YLENE; The ester class is such as ETHYLE ACETATE, isopropyl acetate, methyl aceto acetate, pentyl acetate, isobutyl isobutyrate and jasmal; Ethers is such as ether, o-butyl ether, THF and 1,4-diox; Glycol ethers is such as glycol monomethyl methyl ether, terepthaloyl moietie monomethyl ether acetate, diglycol monotertiary butyl ether and Ucar 35 list phenyl ether; Ketone is such as acetone, methyl ethyl ketone, pimelinketone, Pyranton, Methyl amyl ketone and diisobutyl ketone; Petroleum hydrocarbon is such as gasoline, petroleum naphtha, kerosene, diesel oil, heavy oil and crude oil; Lubricating oil is such as spindle oil and turbine oil; And organic oil.
When but absorption fluids was organic oil, it can be selected from any organic oil that is applicable to preparation individual, family expenses or health care preparation known in the art.The organic oil that is fit to includes but not limited to that natural oil is such as Oleum Cocois, Semen Maydis oil, VT 18, sweet oil, rapeseed oil, Oleum Gossypii semen, sardine oil, menhaden fish oil and whale oil; Hydro carbons is such as MO and Parleam; Fatty Alcohol(C12-C14 and C12-C18) is such as Standamul G; The ester class is such as phenylformic acid C12-C15 alkyl ester; The diester class is such as propylene glycol dipelargonate (propylene dipelarganate); With three ester classes, such as capryiin.The organic oil component can also be the mixture of low viscosity oil and heavy oil.The low viscosity oil that is fit to has the viscosity at 25 ℃ following 5 to 100mPas, and normally has the ester of structure RCO-OR ', and wherein RCO represents the carboxylic acid group, and wherein OR ' is pure residue.The instance of the low viscosity oil that is fit to includes but not limited to, the mixture of Salacos 913, PEG-4 two heptanoates, PIVALIC ACID CRUDE (25) isooctadecanol ester, PIVALIC ACID CRUDE (25) 13 esters, sad hexadecyl ester, cetyl palmitate, ricinolic acid hexadecyl ester, Triple Pressed Stearic Acid hexadecyl ester, tetradecanoic acid hexadecyl ester, two caprylic/capric cocoyl esters, Unimac 5680 ester in the last of the ten Heavenly stems, Isodecyl oleate, Isodecyl Neopentanoate, PIVALIC ACID CRUDE (25) dissident ester, Wickenol 155, oxysuccinic acid dioctyl ester, sad 13 esters, Tetradecyl tetradecanoate, Standamul G or Standamul G, Acetylated lanolin alcohols, cetyl acetate, Permethyl 99A. alcohol, polyglyceryl-3-diisopstearate or its mixture.
The heavy oil that is fit to has at 25 ℃ of following 200-1 usually, and 000, the viscosity of 000mPas, alternatively 100,000-250, the viscosity of 000mPas.The instance of the heavy oil that is fit to includes but not limited to Viscotrol C, yolk and lanolin derivative, Hydrocerol A three isocetyl esters, sorbitan sesquioleate, C10-18 triglyceride level, caprylic/capric/triglyceride level, Oleum Cocois, Semen Maydis oil, Oleum Gossypii semen, oxystearic acid glyceryl triacetyl ester, ricinoleic acid glyceryl triacetyl ester, capryiin, THIXCIN, linseed oil, ermine oil, sweet oil, plam oil, mist ice grass grease, rapeseed oil, VT 18, sunflower seed oil, tallow, tricaprin, trihydroxy-tristearin, three different tristearins, Trilauroylglycerol, trilinolein, trimyristin, triolein, tripalmitin, tristearin, Walnut oil., wheatgerm oil, SUV or its mixture.
But other organic cpds that are suitable for absorption fluids include but not limited to, MO such as whiteruss or liquid petroleum; Animal oil such as perhydro shark alkene oil; Vegetables oil such as sweet apricot oil, thick shell oil, plam oil, Viscotrol C, Avocado Oil, jojoba oil, sweet oil or grain germ oil; The ester class of lanoceric acid, oleic acid, LAURIC ACID 99 MIN, Triple Pressed Stearic Acid or tetradecanoic acid; Alcohols such as oleyl alcohol, inferior oleyl alcohol or linolenyl alcohol, isooctadecanol or Standamul G; Ethanoyl glyceryl ester, octanoate, decylate or ricinoleate with alcohols or polyvalent alcohol.Alternatively, can use at 25 ℃ to be the solid winterized stearin, such as THIXCIN, plam oil or Oleum Cocois or hydrogenated tallow; Monoglyceride, triglyceride, triglyceride level or sucrose glyceride; Yolk; Or be the solid fatty ester at 25 ℃.
Organic oil can also be a volatile organic solvent.What be suitable as the volatile organic solvent component is multiple C8-C20 isoparaffin, such as C12 isoparaffin or the C12 isoparaffin (Permethyl 99A.) with trade(brand)name
99A made by Permethyl Corporation.Commercial obtainable multiple C16 isoparaffin also is fit to such as NSC 109495.Other volatile solvents that are fit to are multiple fluorine materials, such as ethyl perfluor ethyl isobutyl ether (with) ethyl perfluor butyl ether (3MCosmetic fluid CF-76) and Cosmetic Fluid CF-61: methyl perfluor ethyl isobutyl ether (with) methyl perfluor butyl ether (3M Cosmetic Fluid CF-61).
Organic cpds also can be selected from acetonitrile, Nitromethane 99Min., N, propylene oxide, trioctyl phosphate, GBL, furfural, pine-tree oil, turps and meta-cresol; The volatility seasonings; With other available seasoningss, comprise aldehydes and ester class; Volatile spice is such as natural product and perfume oil.Organic can miscible fluid can be single mixture of planting compound or compound.In addition, but absorption fluids can be organic can miscible fluid and other can miscible fluid such as siloxanes mixture.
In some embodiments, but absorption fluids can be the ionic fluid.The ionic fluidic instance that is fit to includes but not limited to; Imdazole derivatives is such as 1-ethyl-3-methyl toluenesulphonic acids imidazoles, 1-ethyl-3-methyl Tetrafluoroboric acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride, 1-vinyl-3-ethyl-phosphofluoric acid imidazoles, 1-butyl-3-methyl phosphofluoric acid imidazoles; And pyridine derivate, such as 1-butyl-4-methyl chloropyridine, 1-butyl-4-methyl phosphofluoric acid pyridine and 1-butyl-4-methyl Tetrafluoroboric acid pyridine.
In some embodiments, but absorption fluids can be a supercutical fluid.The instance of the supercutical fluid that is fit to includes but not limited to, supercritical co, supercritical water, overcritical ethane, the inferior nitrogen of supercritical oxidation, supercritical ammine; Overcritical 1,1,1, the 2-Tetrafluoroethane; Overcritical methylene fluoride; Overcritical pentafluoride ethane; And composition thereof.The solvent strength of supercutical fluid also can be adjusted by many cosolvent such as methyl alcohol, ethanol, acetone, hexane or benzene.
But the instance that is used for the absorption fluids that is fit to of the polymerisable YSR 3286 of polymerization free radical includes but not limited to, hexane, hexanaphthene, heptane, SWS-F 221, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, decamethyl tetrasiloxane, Permethyl 99A., NSC 109495, Isodecyl Neopentanoate, isononyl isononanoate, isoparaffin, isoalkane and capryloyl methyl trisiloxanes, toluene, ETHYLE ACETATE, 1-vinyl-3-ethyl-phosphofluoric acid imidazoles, tetrapropyl-four cyano ammonium borate and have at 25 ℃ of polydimethylsiloxane fluid or its mixtures less than the trimethylsilyl-terminated of the viscosity of 1000cP.In some embodiments, but the polydimethylsiloxane fluid that is elected to be the trimethylsilyl-terminated of absorption fluids have at 25 ℃ from about viscosity of 0.5 to about 100cP.
, obtained good result through selecting straight chain and annular siloxane such as decamethylcyclopentaandoxane, Permethyl 99A. and NSC 109495 although but many absorption fluids can be suitable for swelling silicone polymer particulate.
Personal care and health care products
Silicon-ketone composition of the present invention can be used for multiple application, such as being used for personal care and health care products.For example, such compsn can be used on following in: reodorant; Antiperspirant; Antiperspirant/deodorant; Article shave; Skin care product such as lotion, moistening agent and toner; Articles for shower; Cleaning product; Hair care product such as shampoo, hair conditioner, mousse, shaping glue, hair spray, hair dye, hair dyeing product, bleached hair agent, curly hair product (waving product) and straight hair cream; Repair first product such as nail varnish, nail polish remover, nail polish paste and lotion and stratum corneum tenderizer; Protection cream such as sunscreen, sterilant and anti-aging product; Makeup such as lipstick, foundation cream, face powder, eyeliner, eye shadow, rouge (blush), color make-up, Mascara; The Metabolism Vitamins and Hormones carrier; Fragrance carrier; Wherein add other personal care formulations of silicone component routinely and be used for the part and apply drug delivery system the pharmaceutical composition that puts on skin.
For example, silicon-ketone composition of the present invention can be used for improving the characteristic of following material: protective skin cream, skin-care liquid, moistening agent, facial-care article such as acne or wrinkle remover, individual and facial cleansing agent, bath oil, perfume, Gu Longshui, sachet, sunscreen, shave preceding and aftershave lotion, liquid soap, shaving soap, shaving foam, shampoo, hair conditioner, hair spray, mousse, agent for permanent hair waving, trichogen, stratum corneum maintenance plain (cuticle coat) and makeup.The instance of their purposes in makeup is dye leveller and the diffusant as the pigment in makeup, color make-up, foundation cream, rouge, lipstick, lip oil, eyeliner, Mascara, makeup removing oil, color make-up makeup removing agent and the powder.
In a plurality of embodiments, silicone elastomer paste of the present invention can be used on the personal care that is used for the mankind or animal and health care products with humidification, dyeing, with common improvement outward appearance or to apply activeconstituents such as opalizer, reodorant and sterilant.For example, they can be used as thickening material, like US6, and 051,216, instruction among US 5,919,441 and the US 5,981,680; Be used to construct oils, as disclosed among WO 2004/060271 and the WO 2004/060101; Be used in the sunscreen composition, like what instruct among the WO 2004/060276; As the structurising agent (structuring agent) in the cosmetic composition that also comprises film-forming resin, as disclosed among the WO 03/105801; Be used in the cosmetic composition, like US2003/0235553, US2003/0072730, US2003/0170188, EP 1,266; 647, EP 1,266, and 648, EP 1; 266,653, instruct among WO 03/105789, WO 2004/000247 and the WO03/106614; As structurising agent, like what instruct among the WO 2004/054523; Be used in the attrition resistant cosmetic composition, like what instruct among the US2004/0180032: be used in transparent or semitransparent nursing and/or the cosmetic composition, like what discuss among the WO 2004/054524; All these incorporates this paper by reference into.
Silicone elastomer paste of the present invention can be used on and includes but not limited to rod, soft solid, rolls in the antiperspirant and deodorant products of the formula of putting on the skin (roll on), aerosol and pump Sprayable.For example, such antiperspirant and deodorant products can comprise following as activeconstituents: ammonium chloride, tetrachloro hydroxyl aluminium zirconium GLY, tetrachloro hydroxyl aluminium zirconium PEG, chlorination hydroxyl aluminium, tetrachloro hydroxyl aluminium zirconium PG, chlorination hydroxyl aluminium PEG, trichlorine hydroxyl aluminium zirconium, chlorination hydroxyl aluminium PG, trichlorine hydroxyl aluminium zirconium GLY, Hexachlorophene, benzalkonium chloride, sesquialter chlorination hydroxyl aluminium, sodium hydrogencarbonate, sesquialter chlorination hydroxyl aluminium PEG, CHLOROPHYLLINE-copper composition, triclosan, eight chlorine hydroxyl aluminium zirconium and zinc ricinoleates.
Personal care of the present invention and health care products can be the forms with cream, gel, powder, paste or the liquid that can freely topple over.Usually, be the solid material as not existing in room temperature in the fruit product, so such product can use simple propeller mixer, Brookfield reverse rotation mixing tank or the preparation of intimate mixing device in room temperature usually.Usually do not require special devices or processing conditions.The formal category that depends on manufacturing, the preparation method is with difference, but such method is well known in the art.
Personal care of the present invention and health care products can be used through standard method; Such as using applicator, brush that they are put on human body such as skin or hair; Apply with hand, topple over them and/or wipe possibly or massage product on health or in the health.The removal method, the removal method that for example is used for color make-up also is known standard method, comprises washing, wiping and divests.For on skin, using, personal care and health care products can be used in a usual manner, for example are used for conditioning skin.To put on skin for the significant quantity product of this purpose.Such significant quantity is usually from about 1mg/cm
2To about 3mg/cm
2Change.Putting on skin generally includes said composition is processed into skin.This method that puts on skin may further comprise the steps: skin is contacted with the product of significant quantity and then product is rubbed into skin.Can be as repeat these steps requiredly repeatedly to realize the expectation benefit.
For on hair, using, personal care and health care products can be used in a usual manner, for example are used for conditioning hair.To put on hair for the significant quantity product of this purpose.Such significant quantity usually from about 1g to about 50g, alternatively from the extremely about 20g variation of about 1g.Put on hair and generally include this product treatment is spreaded all over hair, make great majority or all hairs contact with this product.This method that puts on hair may further comprise the steps: hair is contacted with the product of significant quantity and then product treatment spreaded all over hair.Can be as repeat these steps requiredly repeatedly to realize the expectation benefit.
In some embodiments, personal care of the present invention and health care products are selected from antiperspirant, reodorant, protective skin cream, skin-care liquid, moistening agent, facial-care article, facial cleansing article, bath oil, perfume, Gu Longshui, sachet, sunscreen, the preceding lotion that shaves, aftershave lotion, liquid soap, body wash, solid soap, shaving soap, shaving foam, shampoo, hair conditioner, hair dye, hair spray, mousse, agent for permanent hair waving, trichogen, stratum corneum maintenance element, makeup, color make-up, foundation cream, rouge, lipstick, lip oil, eyeliner, Mascara, eye shadow, makeup removing oil and color make-up makeup removing agent.
Embodiment
Through will understanding the present invention better with reference to following examples, the mode through example provides following examples, and it will be appreciated by those skilled in the art that they are unexpectedly for restrictive.
Comprise the separation of the polymer particles of methylmethacrylate copolymer
In the Vestolen PP 7052 cup; Methacrylic ester (the α that 4.75g is had number-average molecular weight (Mn) and about 2.0 the polymolecularity of 8200g/mol; ω-methacryloxypropyl dimethylsilane oxygen base) end capped YSR 3286 (PDMS) (MA-PDMS) adds to mole such as 0.26g TEB 3K and 0.15g boron triethyl-propanediamine mixtures (TEB-PDA), and in FlackTek SpeedMixer, mixes 15 seconds.Add 0.08g Tergitol-15-s-3 and mixed 15 seconds to content, add 0.41g Tergitol-15-s-40 subsequently and mixed 15 seconds.Add the 0.28g deionized water then and mixed 15 seconds.Add other 20ml water with the 2ml increment, mix forming O/w emulsion in 15 seconds behind each increment.Emulsion content is dropwise added to the solution that comprises 0.08g acetate and 19.63g water in the vial, cause the formation and the deposition of polymer particles.Utilization is based on the aspirator of the tap particle through the isolated by vacuum filtration gained, in vacuum drying oven, spends the night at 25 ℃ of pressure oven dryings with<25mm Hg then.Except as otherwise noted, use identical oven drying condition otherwise among all embodiment subsequently.
Embodiment 2
Comprise the separation of the polymer particles of stearyl methacrylate multipolymer
In the Vestolen PP 7052 cup, 4.77g MA-PDMS is added to 0.26g stearyl methacrylate and 0.17g TEB-PDA, and in FlackTek SpeedMixer, mixed 15 seconds.Add 0.07g Tergitol-15-s-3 and mixed 15 seconds to content, add 0.42g Tergitol-15-s-40 subsequently and mixed 15 seconds.Add the 0.29g deionized water then and mixed 15 seconds.Add other 20ml water with the 2ml increment, mix forming O/w emulsion in 15 seconds behind each increment.Emulsion content is dropwise added to the solution that comprises 0.08g acetate and 19.45g water in the vial, cause the formation and the deposition of polymer particles.Pass through the particle and the oven drying of isolated by vacuum filtration gained as described above.
Embodiment 3
Comprise the separation of the polymer particles of multiple multipolymer
In the Vestolen PP 7052 cup, will in FlackTek SpeedMixer, mix 15 seconds as the 0.08gTergitol-15-s-3 and the 0.42g Tergitol-15-s-40 of cosurfactant and tensio-active agent.Add 4.77g MA-PDMS, 0.16g TEB-PDA, 0.25g methyl acrylate and 0.30g initial water, and each back of adding was mixed 15 seconds.Add other 20ml water to content with the 2ml increment, mix forming emulsion in 15 seconds between the increment.Then emulsion content is transferred in the vial that holds 0.05g acetate, 20.75g deionized water and stirring rod.Allow example reaction, and spend the night through vacuum filtration recovery particle and oven drying saidly like embodiment 1.
Use displaced comonomer to carry out same program, and amount is shown in Table 1.
Table 1
Embodiment 4
Comprise the separation of the polymer particles of Rocryl 400 multipolymer
In the Vestolen PP 7052 cup, will in FlackTek SpeedMixer, mix 15 seconds as the 0.08gTergitol-15-s-3 and the 0.45Tergitol-15-s-40 of cosurfactant and tensio-active agent.Add 0.15g TEB-PDA, 0.26g HEMA (methylacrylic acid 2-hydroxyl ethyl ester) and 4.76g MA-PDMS to content, and each back of adding was mixed 15 seconds.Add the 0.26g initial water then and mixed 15 seconds, and add other 20ml water, mixed 15 seconds between the increment with the 2ml increment.Then five milliliters of contents are transferred in the vial that holds 0.06g acetate, 20.02g deionized water and stirring rod, and allow reaction and follow stirring.Spend the night through vacuum filtration recovery particle and oven drying like embodiment 1 saidly.
Embodiment 5
Comprise the separation of the polymer particles of Rocryl 400 multipolymer
In the Vestolen PP 7052 cup, will in FlackTek SpeedMixer, mix 15 seconds as the 0.08gTergitol-15-s-3 and the 0.45Tergitol-15-s-40 of cosurfactant and tensio-active agent.Add 0.15g TEB-PDA, 0.26g HEMA (methylacrylic acid 2-hydroxyl ethyl ester) and 4.76g MA-PDMS to content, and each back of adding was mixed 15 seconds.Add the 0.26g initial water then and mixed 15 seconds, and add other 20ml water, mixed 15 seconds between the increment with the 2ml increment.Five milliliters of contents are added to the vial that holds 0.07g vinylformic acid and 18.91g water, and allow to react and follow with 200rpm and stir.Spend the night through vacuum filtration recovery particle and oven drying like embodiment 1 saidly.
Embodiment 6
Comprise the separation of the polymer particles of Rocryl 400 multipolymer
In the Vestolen PP 7052 cup, acetate is added to methylacrylic acid 2-hydroxyl ethyl ester (HEMA) and MA-PDMS and in FlackTek SpeedMixer, mixed 30 seconds.Tensio-active agent Tergitol-15-s-40 and cosurfactant Tergitol-15-s-3 are added in the mixture together with initial water and mixed other 30 seconds.Then through following dilution content: the water of interpolation 2ml increment also mixed 30 seconds behind each increment, added 15ml altogether, and wherein last increment is 3ml.Emulsion is transferred to the clean beaker of holding stirring rod, and add the TEB-PDA initiator.Allow example reaction 2 hours, afterwards, reclaim particle and vacuum drying oven dried overnight through vacuum filtration saidly like embodiment 1.The composition of sample is listed in table 2.
Table 2.
All values all is that quality and unit are in gram.
Embodiment 7
Comprise the separation of the polymer particles of Rocryl 400 multipolymer
In the Vestolen PP 7052 cup, acetate is added to methylacrylic acid 2-hydroxyl ethyl ester (HEMA) and MA-PDMS and in FlackTek SpeedMixer, mixed 30 seconds.The trimethyl silicone hydride silicate (PGMTSS) of surfactant polyethylene modification is added in the mixture together with initial water and mixed other 30 seconds.Then through following dilution content: the water of interpolation 2ml increment also mixed 30 seconds behind each increment, added 15ml altogether, and wherein last increment is 3ml.Emulsion is transferred to the clean beaker of holding stirring rod, and add the TEB-PDA initiator.Allow example reaction 2 hours, afterwards, reclaim particle and vacuum drying oven dried overnight through vacuum filtration saidly like embodiment 1.The composition of sample is listed in table 3.
Table 3
All values all is that quality and unit are in gram.
EELS to PDMS and HEMA copolymerization particle (sample formulation shown in the table 4) analyzes expression, and particle is the nanophase that is isolated in the territory of being rich in pHEMA that intersperses among in the PDMS matrix.Through representing, there is about 21% HEMA in the PDMS matrix in observed EELS zone to apply the quantitative phasor (not shown) that multiple least square fitting (multiple least square fit) obtains from the core energy of pure component and particle specimens forfeiture signal.In the details in a play not acted out on stage, but told through dialogues STEM of granule interior structure image (Fig. 1), disclose than dark contrast in the zone (pHEMA) of light density, and disclose than dark contrast in the zone (PDMS) of heavier density in the light field TEM image (Fig. 2).The result representes, the particulate component does not experience rule as usual and is no silicone agglomerate territory based on being separated on a large scale of emulsion polymerization technology experience of radical, but formation is included in the microfacies-isolating particle that is rich in organic territory in the continuous silicone ketone group matter.And consistent between theoretical monomer load and the actual granulometric composition provides copolymerization efficient high confirmation.
Table 4.EELS sample formulation
Content | Quality (g) | By gross weight |
HEMA | 1.03 | 4.13 |
MA-PDMS | 4.03 | 16.12 |
TEB-PDA | 0.16 | 0.64 |
Tergitol-15-s-40 | 0.45 | 1.78 |
Tergitol-15-s-3 | 0.09 | 0.35 |
Initial water | 0.28 | 1.12 |
Other water | 20.00 | 79.98 |
Amount to | 25.00 | 100.00 |
Embodiment 8
Use the separation of TEB-BI as the polymer particles of radical initiator
In the Vestolen PP 7052 cup, add 0.46g Tergitol-15-s-40 and 0.08g Tergitol-15-s-3 as tensio-active agent and cosurfactant and mixing 15 seconds in FlackTek SpeedMixer.Add TEB-BI (boron triethyl-NSC 158165) that 0.16g comprises 4.6wt% boron as initiator, and mixed 15 seconds.Add 4.78g MA-PDMS and 0.29g methylacrylic acid 2-hydroxyl ethyl ester to content, and each back of adding was mixed 15 seconds.Add 0.28g water then and mixed 15 seconds, and add other 20ml water, mixed 15 seconds behind each increment with the 2ml increment.Be used for reaction with sample transfer to cleaning glass bottle and to sample interpolation 0.06g acetate.Reclaim particle and oven drying through vacuum filtration like embodiment 1 saidly.
Embodiment 9
Use the separation of TEB-MOPA as the polymer particles of radical initiator
In the Vestolen PP 7052 cup, 0.42g Tergitol-15-s-40 and 0.08g Tergitol-15-s-3 were mixed 15 seconds in FlackTek SpeedMixer.Add 0.15g TEB-MOPA (boron triethyl-methoxy propanamine), 4.80g MA-PDMS, 0.25g HEMA and 0.35g water to content, and between adding, mixed 15 seconds.Add other water with the 2ml increment, mixed 15 seconds behind each increment, add 20ml altogether.Five ml mixtures are transferred to the cleaning bottle, and add 0.06g acetate and stir with 200rpm.Reclaim particle and oven drying through vacuum filtration like embodiment 1 saidly.
Use the separation of palmityl trimethyl ammonium chloride as the polymer particles of emulsifying agent
In the Vestolen PP 7052 cup, interpolation 9.51g MA-PDMS, 0.53g methylacrylic acid 2-hydroxyl ethyl ester, 0.23g TEB-PDA also mixed 15 seconds in FlackTek SpeedMixer.Add the 0.67g 25wt% palmityl trimethyl ammonium chloride aqueous solution (Fluka purum CAS#112-02-7) and 0.31g water to content, and each back of adding was mixed 15 seconds.With~the other 15ml water of 2ml increment interpolation, and behind each increment, mixed 15 seconds.Content is transferred to 4 ounces of squat vials and adds 0.08g acetate and stirring rod, and agitating plate is arranged on 250rpm.Reclaim particle and oven drying through vacuum filtration like embodiment 1 saidly.
Embodiment 11
Use the separation of Arquad 16-19 as the polymer particles of emulsifying agent
In the Vestolen PP 7052 cup, interpolation 4.79g MA-PDMS and 0.26g HEMA also mixed 15 seconds in FlackTek SpeedMixer.To content add 0.11g TEB-PDA and 0.34g ethoxylation quaternary ammonium salt solution (Arquad-16-19, Akzo-Nobel), and mixing 15 seconds between each the interpolation.Add 0.24g water then and mixed 15 seconds.Add other 20ml water with the 2ml increment, and behind each increment, mixed 15 seconds.Content is transferred to 4 ounces of vials and adds 0.04g acetate and stirring rod, and allow at the 200rpm stirred sample.Reclaim particle and oven drying through vacuum filtration like embodiment 1 saidly.
Embodiment 12
Use the separation of the polymer particles of ETHYLE ACETATE cosolvent
In the Vestolen PP 7052 cup; Add 1.09g
ACR-D2, promptly polyfunctional propenoate silicone prepolymer (Siltech Corporation) and 0.52g methylacrylic acid 2-hydroxyl ethyl ester and 0.26g ETHYLE ACETATE also mixed 15 seconds in FlackTek SpeedMixer.Add 0.03gTEB-PDA, 0.19g Tergitol-15-s-40,0.07g Tergitol-15-s-3 and 0.25g water and mixed 15 seconds to content.Add other water with following increment: 0.25g, 1.03g, 2.69g, 2.07g, 2.18g and 2.23g, and mix each back of adding.Add about 0.17g vinylformic acid and allow reaction, stir with 350rpm simultaneously.Use
ACR Di-100, other components of promptly a kind of YSR 3286 of acrylate ended of 255cP viscosity (Siltech Corporation) and different concns as described in Table 5 repeat this program.
Table 5.
Embodiment 13
The purposes of silicone paste in antiperspirant
With 0.31g phenylformic acid C12-15 alcohol ester (Finsolv TN, Finetex, Inc.); 2.50g elastomerics paste (12% elastomerics among the D5 is equivalent to 5wt%HEMA/PDMS particle and the 3.29g decamethyl five rings siloxanes (D5) of the 0.45g that mixes); 3.36g dimethicone and trisiloxanes fluidic mixture (30-60% decamethyl tetrasiloxane, CAS registration number 141-62-8; The 30-60% octamethyltrisiloxane, CAS registration number 107-51-7; 15-40% ten dimethyl-five siloxanes, CAS registration number 141-63-9); 0.10g have the crosslinked dimethicone/vinyl dimethicone crosspolymers particulate powder of 5 μ m median sizes; With the active antiperspirant of 2.50g be that tetrachloro hydroxyl aluminium zirconium-gly (REACH AZP 908SUF) utilizes FlackTek SpeedMixer to mix 15 seconds.Antiperspirant sample performance particle quality and the viscosity more lower slightly than the control sample of in subsequent embodiment, listing.
Through following preparation reference composition: with 0.30g phenylformic acid C12-15 alcohol ester (Finsolv TN, Finetex, Inc.); 3.74g according to US 6,770, the platinum solidified silicone elastomer paste that the program of the embodiment 6 of 708B2 is made; 3.36g dimethicone and trisiloxanes fluid mixture (30-60% decamethyl tetrasiloxane, CAS registration number 141-62-8; The 30-60% octamethyltrisiloxane, CAS registration number 107-51-7; 15-40% ten dimethyl-five siloxanes, CAS registration number 141-63-9); 0.10g have the crosslinked dimethicone/vinyl dimethicone crosspolymers particulate powder of about 5 μ m median sizes; With the active antiperspirant of 2.55g be that tetrachloro hydroxyl aluminium zirconium-gly (REACH AZP908SUF) utilizes FlackTek SpeedMixer to mix 30 seconds.The antiperspirant of gained be quality arranged and have a medium-viscosity.
Embodiment 14
The characteristic of polymer particles and l-vinyl-2-pyrrolidone are as the proof of the purposes of hydrophilic co-monomer
The MA-PDMS of 3.00g part is joined 40ml Vestolen PP 7052 cup with 2.00g l-vinyl-2-pyrrolidone and 0.14gTEB-PDA initiator.Biased sample is 30 seconds in FlackTek SpeedMixer.Add 0.07g Tergitol 15-S-3,0.18g Tergitol 15-S-40 and 0.31g water then.Other 30 seconds of biased sample.Add other 15g water with the 2g increment, and mixed 20 seconds between adding.Dropwise add 0.09g acetate to emulsion, go up at dental mixing tank (dental mixer) subsequently and mixed 30 seconds.Adding stirring rod to sample also allows on agitating plate, to mix 2 hours.Utilization is reclaimed particle through the vacuum filtration of Mierocrystalline cellulose filter paper.With particle in vacuum drying oven with~35-50 ℃ dried overnight.Transmission optics microscopy (Zeiss Axioskop) and SEM (JEOL JSM-6335FE-SEM) disclose diameter from~spheroidal particle that the 10-100 micron changes.ATR-IR (being equipped with the Thermo Nicolet 6700 of Smart MIRacle ATR annex) confirms the existence of hydrophile copolymers, and~1660cm
-1Absorbancy increase.
Embodiment 15
The characteristic of polymer particles and DMAEMA are as the proof of the purposes of hydrophilic co-monomer
The MA-PDMS of 4.00g part is joined 40ml Vestolen PP 7052 cup with 1.00g dimethylaminoethyl methacrylate (DMAEMA) and 0.13g TEB-PDA initiator.Biased sample is 30 seconds in FlackTek SpeedMixer.Add 0.08g Tergitol 15-S-3,0.20g Tergitol 15-S-40 and 0.31g water then.Other 30 seconds of biased sample.Add other 15g water with the 2g increment, and mixed 20 seconds between adding.Dropwise add 0.09g acetate to emulsion, on the dental mixing tank, mixed 30 seconds subsequently.Adding stirring rod to sample also allows on agitating plate, to mix 2 hours.Utilization is reclaimed particle and particle is spent the night with the pressure drying of<25mm Hg between with 35-50 ℃ in vacuum drying oven through the vacuum filtration of Mierocrystalline cellulose filter paper.Optical microscopy discloses diameter from~spheroidal particle that the 10-100 micron changes.ATR-IR confirms the existence of hydrophile copolymers, and~1730cm
-1Absorbancy increase.
Embodiment 16
The characteristic of polymer particles and n-vinyl formamide are as the proof of the purposes of hydrophilic co-monomer
The MA-PDMS of 3.50g part is joined 40ml Vestolen PP 7052 cup with 1.50g n-vinyl formamide and 0.13gTEB-PDA initiator.Biased sample is 30 seconds in FlackTek SpeedMixer.Add 0.10g Tergitol 15-S-3,0.23g Tergitol 15-S-40 and 0.33g water then.Other 30 seconds of biased sample.Add other 15g water with the 2g increment, and mixed 20 seconds between adding.Dropwise add 0.09g acetate to emulsion, on the dental mixing tank, mixed 30 seconds subsequently.Adding stirring rod to sample also allows on agitating plate, to mix 2 hours.Add a part of methyl alcohol to help to break emulsion and centrifugal solution to sample.It is divided into multilayer, and reclaims particle and vacuum filtration and with methanol rinse then.With particle such as embodiment 16 dried overnight in vacuum drying oven saidly.Optical microscopy and SEM disclose diameter from~spheroidal particle that the 10-100 micron changes.ATR-IR confirms the existence of hydrophile copolymers, and~1660cm
-1Absorbancy increase.
Embodiment 17
Separation with polymer particles of vinylpyridine copolymer
The MA-PDMS of 4.50g part is joined 40ml Vestolen PP 7052 cup with 0.50g 4-vinylpridine and 0.15g TEB-PDA initiator.Biased sample is 30 seconds in FlackTek SpeedMixer.Add 0.08g Tergitol 15-S-3,0.19g Tergitol 15-S-40 and 0.32g water then.Other 30 seconds of biased sample.Add other 15g water with the 2g increment, and mixed 20 seconds between adding.Dropwise add 0.09g acetate to emulsion, on the dental mixing tank, mixed 30 seconds subsequently.Adding stirring rod to sample also allows on agitating plate, to mix 2 hours.Utilization is reclaimed particle through the vacuum filtration of Mierocrystalline cellulose filter paper.With particle such as embodiment 16 dried overnight in vacuum drying oven saidly.
Embodiment 18
The characteristic of polymer particles and N, N ,-DMAA is as the proof of the purposes of hydrophilic co-monomer
With the MA-PDMS and the 2.50g N of 2.50g part, N,--DMAA and 0.14gTEB-PDA initiator join 40ml Vestolen PP 7052 cup together.Biased sample is 30 seconds in FlackTek SpeedMixer.Add 0.07g Tergitol 15-S-3,0.18g Tergitol 15-S-40 and 0.31g water then.Other 30 seconds of biased sample.Add other 15g water with the 2g increment, and mixed 20 seconds between adding.Dropwise add 0.09g acetate to emulsion, on the dental mixing tank, mixed 30 seconds subsequently.Adding stirring rod to sample also allows on agitating plate, to mix 2 hours.Use the toluene centrifugal pellet.Solution is divided into multilayer, and reclaims particle and vacuum filtration and with methanol rinse then.With particle such as embodiment 16 dried overnight in vacuum drying oven saidly.Optical microscopy and SEM disclose the spheroidal particle that is partly covered by the irregularly shaped chip that possibly be homopolymer.ATR-IR confirms the existence of hydrophile copolymers, and~1630cm
-1Absorbancy increase.
Embodiment 19
The characteristic of polymer particles and N-NSC 11448 are as the proof of the purposes of hydrophilic co-monomer
The MA-PDMS of 2.50g part is joined 40ml Vestolen PP 7052 cup with 2.50g N-NSC 11448 and 0.13gTEB-PDA initiator.Biased sample is 30 seconds in FlackTek SpeedMixer.Add 0.08g Tergitol 15-S-3,0.21g Tergitol 15-S-40 and 0.27g water then.Other 30 seconds of biased sample.Add other 15g water with the 2g increment, and mixed 20 seconds between adding.Dropwise add 0.09g acetate to emulsion, on the dental mixing tank, mixed 30 seconds subsequently.Adding stirring rod to sample also allows on agitating plate, to mix 2 hours.Reclaim particle through vacuum filtration, with methanol rinse, and like embodiment 16 dried overnight in vacuum drying oven saidly.Optical microscopy and SEM disclose diameter from~spheroidal particle that the 10-100 micron changes.ATR-IR confirms the existence of hydrophile copolymers, and~1645cm
-1Absorbancy increase.
The proof of the purposes of numerous emulsifiers
The MA-PDMS of 2.51g part is joined 40ml Vestolen PP 7052 cup with 2.50g N-NSC 11448 (IPAA) and 0.13g TEB-PDA initiator.Biased sample is 30 seconds in FlackTek SpeedMixer.Add 0.24g PGMTSS and 0.31g water then.Other 30 seconds of biased sample.With~the other 15g water of 2g increment interpolation, and mixed 20 seconds between adding.Dropwise add 0.09g acetate to emulsion, on the dental mixing tank, mixed 30 seconds subsequently.Adding stirring rod to sample also allows on agitating plate, to mix 2 hours.Use the toluene centrifugal pellet.Solution is divided into multilayer, and reclaims particle and vacuum filtration and with methanol rinse then.With particle such as embodiment 16 dried overnight in vacuum drying oven saidly.Optical microscopy and SEM disclose diameter from~spheroidal particle that the 10-100 micron changes.ATR-IR confirms the existence of hydrophile copolymers, and~1645cm
-1Absorbancy increase.Transmission electron microscopy (TEM) indication has taken place to be separated in the rank of 100nm, has confirmed to comprise the two multipolymer of phase that is rich in the hydrophilic organic thing and the hydrophobic phase that is rich in silicon and has not been separated by macroface.
Embodiment 21
The proof of the purposes of non-sour organonitrogen reactive compounds
The MA-PDMS of 2.50g part is joined 40ml Vestolen PP 7052 cup with 2.50g IPAA and 0.13g TEB-PDA initiator.Biased sample is 30 seconds in FlackTek SpeedMixer.Add 0.24g PGMTSS and 0.26g water then.Other 30 seconds of biased sample.With~the other 15g water of 2g increment interpolation, and mixed 20 seconds between adding.Dropwise add the 0.12g carbonic acid glyceride to emulsion, on the dental mixing tank, mixed 30 seconds subsequently.Adding stirring rod to sample also allows on agitating plate, to mix 2 hours.As if reaction than carrying out slowly with acidolysis mixture (acid decomplexer), but particle size with output the particle size during with use acetate similar with output.Use the methyl alcohol centrifugal pellet.Solution is divided into multilayer, and reclaims particle and vacuum filtration and with methanol rinse then.With particle such as embodiment 16 dried overnight in vacuum drying oven saidly.Optical microscopy and SEM disclose diameter from~spheroidal particle that the 10-100 micron changes.ATR-IR confirms the existence of hydrophile copolymers, and~1645cm
-1Absorbancy increase.
Embodiment 22
The proof of the purposes of non-sour organonitrogen reactive compounds
The MA-PDMS of 2.50g part is joined 40ml Vestolen PP 7052 cup with 2.50g N-NSC 11448 and 0.13gTEB-PDA initiator.Biased sample is 30 seconds in FlackTek SpeedMixer.Add 0.26g PGMTSS and 0.27g water then.Other 30 seconds of biased sample.With~the other 15g water of 2g increment interpolation, and mixed 20 seconds between adding.Dropwise add the 0.12g propylene carbonate to emulsion, on the dental mixing tank, mixed 30 seconds subsequently.Adding stirring rod to sample also allows on agitating plate, to mix 2 hours.As if reaction than carrying out slowly with the acidolysis mixture, but particle size with output the particle size during with use acetate similar with output.The water centrifugal pellet.Solution is divided into multilayer, and reclaims particle and vacuum filtration and with methanol rinse then.With particle such as embodiment 16 dried overnight in vacuum drying oven saidly.Optical microscopy and SEM disclose diameter from~spheroidal particle that the 10-100 micron changes.ATR-IR confirms the existence of hydrophile copolymers, and~1645cm
-1Absorbancy increase.
Embodiment 23
The proof of compositing range
Preparing several samples with embodiment 20 identical modes, but the MA-PDMS with different ratios makes monomer composition change from 0 to 80wt%IPAA than IPAA.Particularly, the following sample of preparation: (i) 0wt%IPAA; (ii) the MA-PDMS of 19: 1 ratios makes set of monomers become 5wt%IPAA than IPAA; (iii) the MA-PDMS of 9: 1 ratios makes set of monomers become 10wt%IPAA than IPAA; (iv) the MA-PDMS of 4: 1 ratios makes set of monomers become 20wt%IPAA than IPAA; (v) the MA-PDMS of 2.3: 1 ratios makes set of monomers become 30wt%IPAA than IPAA; (vi) the MA-PDMS of 1.5: 1 ratios makes set of monomers become 40wt%IPAA than IPAA; (vii) the MA-PDMS of 1: 4 ratio makes set of monomers become 80wt%IPAA than IPAA.
Fig. 4 shows the thermogravimetric analysis figure that comprises the polymer beads that gathers (dimethyl siloxane-be total to-NSC 11448), and wherein the starting point concentration of IPAA is 0wt%, 10wt%, 20wt%, 40wt% and 80wt%.In air atmosphere, move sample.The particle that only comprises cross-linked silicone has the residue of highest level, because particle forms stable silicate material when being heated.Along with the concentration increase of hydrophile copolymers in the particle, because the hydrocarbon component degradation is a volatile organic matter when being heated, so residue reduces.
Fig. 5 shows the ATR-IR spectrum that comprises the polymer beads that gathers (dimethyl siloxane-be total to-NSC 11448), and wherein the starting point concentration of IPAA changes from 0 to 80wt%.Respectively at 1640cm
-1And 1550cm
-1Acid amides I and acid amides II peak show the corresponding increase that gathers (N-NSC 11448) in the polymer beads.
Fig. 6 shows the dsc (DSC) that comprises the polymer beads that gathers (dimethyl siloxane-be total to-NSC 11448), and wherein the starting point concentration of IPAA changes from 0 to 50wt%.Silicone components has the fusion heat absorption at-50 ℃.Along with the monomeric amount of IPAA in the preparation increases, the endotherm(ic)peak area reduces, and indication gathers (n-NSC 11448) and replaced some siloxanes.The existence that gathers (n-NSC 11448) in the particle is also by indicating in the appearance of~140 ℃ of second-order transition temperatures.
The present invention should not be regarded as being limited to specific embodiment described herein, but is interpreted as containing all embodiments of the present invention.The present invention's multiple modification applicatory and equivalent process and many construction and devices will be easily significantly to those skilled in the art.It will be understood by those skilled in the art that and to carry out multiple change and do not depart from scope of the present invention, those that scope of the present invention is not regarded as being limited in specification sheets, describe.
Claims (38)
1. method for preparing silicon-ketone composition, said method comprises:
(I) polymeric component (A), at least a organopolysiloxane with at least two radical polymerizable groups of average per molecule; And component (B), at least a organic comonomer with at least one radical polymerizable groups of average per molecule; The existence that wherein is aggregated in following component takes place down: component (C), at least a organo-borane radical initiator; Component (D) is with the immiscible at least a non-solvent of component (A); Randomly, component (E), at least a organonitrogen reactive compounds; And oxygen, keep simultaneously from about 5 ℃ of silicone elastomer particulates that form hydrophilic modifying to about 95 ℃ temperature; With
(II) but reclaim said silicone elastomer particulate and they be dispersed at least a absorption fluids and form paste.
2. method according to claim 1, wherein said silicone elastomer particulate is through forming to dispersion-s that comprises component (A), component (B), component (D) and component (E) or emulsion adding component (C).
3. method according to claim 1, wherein said silicone elastomer particulate is through forming to dispersion-s that comprises component (A), component (B), component (C) and component (D) or emulsion adding component (E).
4. method according to claim 1, but wherein said absorption fluids and component (D) immiscible.
5. method according to claim 4, but wherein said absorption fluids is selected from silicone, organic solvent and composition thereof.
6. method according to claim 5, but wherein said absorption fluids is selected from linear siloxanes and cyclosiloxane, C8-C20 isoparaffin, ester class and its combination.
7. method according to claim 6; But wherein said absorption fluids is selected from decamethylcyclopentaandoxane, Permethyl 99A., NSC 109495 or is selected from the mixture of ester class, Standamul G or the Standamul G of Salacos 913, PEG-4 two heptanoates, PIVALIC ACID CRUDE (25) isooctadecanol ester, PIVALIC ACID CRUDE (25) 13 esters, sad hexadecyl ester, cetyl palmitate, ricinolic acid hexadecyl ester, Triple Pressed Stearic Acid hexadecyl ester, tetradecanoic acid hexadecyl ester, two caprylic/capric cocoyl esters, Unimac 5680 ester in the last of the ten Heavenly stems, Isodecyl oleate, Isodecyl Neopentanoate, PIVALIC ACID CRUDE (25) dissident ester, Wickenol 155, oxysuccinic acid dioctyl ester, sad 13 esters, Tetradecyl tetradecanoate, Acetylated lanolin alcohols, cetyl acetate, Permethyl 99A. alcohol, polyglyceryl-3-diisopstearate, and composition thereof.
8. method according to claim 1 wherein remains on temperature from about 10 ℃ to about 35 ℃.
9. method according to claim 1, wherein component (A) is selected from the YSR 3286 and the resin of the functional YSR 3286 of methacrylic ester and resin and acrylate-functional.
10. method according to claim 1; Wherein component (B) is selected from TEB 3K, stearyl methacrylate, methylacrylic acid benzene methyl, methylacrylic acid tetrahydrofuran ester, methylacrylic acid 2-hydroxyl ethyl ester, dimethylaminoethyl methacrylate, N, N-DMAA, n-vinyl formamide, 4-vinylpridine, l-vinyl-2-pyrrolidone, vinylformic acid, methylacrylic acid and N-NSC 11448.
11. method according to claim 1, wherein component (C) is selected from boron triethyl-propanediamine mixture, boron triethyl-NSC 158165 mixture, boron triethyl-methoxy propyl amine compound and three normal-butyl methoxy propyl amine compounds.
12. method according to claim 1, wherein component (D) is selected from water, acetone, methyl alcohol, ethanol and its combination.
13. method according to claim 1, wherein optional components (E) is selected from acetate, Hydrocerol A, vinylformic acid, ROHM and isoflurane chalcone diisocyanate.
14. method according to claim 1; The existence that wherein is aggregated in following component takes place down; Or use following component to handle formed said silicone elastomer particulate: component (F) is applicable at least a activeconstituents of personal care and health care products.
15. method according to claim 1, the existence that wherein is aggregated in following component takes place down: component (G), at least a emulsifying agent.
16. silicone paste according to the preparation of the method for claim 1.
17. silicone paste according to claim 16; But wherein said absorption fluids is selected from decamethylcyclopentaandoxane, Permethyl 99A., NSC 109495 or is selected from the mixture of ester class, Standamul G or the Standamul G of Salacos 913, PEG-4 two heptanoates, PIVALIC ACID CRUDE (25) isooctadecanol ester, PIVALIC ACID CRUDE (25) 13 esters, sad hexadecyl ester, cetyl palmitate, ricinolic acid hexadecyl ester, Triple Pressed Stearic Acid hexadecyl ester, tetradecanoic acid hexadecyl ester, two caprylic/capric cocoyl esters, Unimac 5680 ester in the last of the ten Heavenly stems, Isodecyl oleate, Isodecyl Neopentanoate, PIVALIC ACID CRUDE (25) dissident ester, Wickenol 155, oxysuccinic acid dioctyl ester, sad 13 esters, Tetradecyl tetradecanoate, Acetylated lanolin alcohols, cetyl acetate, Permethyl 99A. alcohol, polyglyceryl-3-diisopstearate, and composition thereof.
18. silicone paste according to claim 16, wherein said paste has 25Pas at least, 40Pas at least alternatively, the viscosity of 100Pas at least alternatively.
19. silicone paste according to claim 16, the wherein said swelling of spheric basically silicone elastomer particulate have the mean diameter from about 0.1 μ m to about 500 μ m.
20. silicone paste according to claim 16, wherein component (A) is selected from the YSR 3286 and the resin of the functional YSR 3286 of methacrylic ester and resin and acrylate-functional.
21. silicone paste according to claim 16; Wherein component (B) is selected from TEB 3K, stearyl methacrylate, methylacrylic acid benzene methyl, methylacrylic acid tetrahydrofuran ester, methylacrylic acid 2-hydroxyl ethyl ester, dimethylaminoethyl methacrylate, N, N-DMAA, n-vinyl formamide, 4-vinylpridine, l-vinyl-2-pyrrolidone, vinylformic acid, methylacrylic acid and N-NSC 11448.
22. silicone paste according to claim 16, wherein component (C) is selected from boron triethyl-propanediamine mixture, boron triethyl-NSC 158165 mixture, boron triethyl-methoxy propyl amine compound and three normal-butyl methoxy propyl amine compounds.
23. silicone paste according to claim 16, wherein component (D) is selected from water, acetone, methyl alcohol, ethanol and its combination.
24. silicone paste according to claim 16, wherein optional components (E) is selected from acetate, Hydrocerol A, vinylformic acid, ROHM and isoflurane chalcone diisocyanate.
25. silicone paste according to claim 16 comprises optional components (F), is applicable at least a activeconstituents of personal care and health care products.
26. silicone paste according to claim 25, wherein component (F) is selected from VITAMINs, opalizer, plant milk extract, spices or essence, part drug's actives, albumen, enzyme, antiperspirant, reodorant, moistening agent, anti-mycotic agent and antiseptic-germicide.
27. silicone paste according to claim 16 comprises optional components (G), at least emulsifying agent.
28. silicone paste according to claim 27, wherein component (G) is selected from Tergitol
TM15-s-3, Tergitol
TM15-s-40, poly ethyldiol modified trimethyl silicone hydride silicate, poly ethyldiol modified siloxanes, poly ethyldiol modified silicon-dioxide, ethoxylated quaternary solution and palmityl trimethyl ammonium chloride solution.
29. personal care product or health care products comprise:
The silicone paste; But it is by the method preparation that is included in the silicone elastomer particulate that disperses hydrophilic modifying at least a absorption fluids; Said silicone elastomer particulate is by comprising following method preparation: polymeric component (A), at least a organopolysiloxane with at least two radical polymerizable groups of average per molecule; And component (B), at least a organic comonomer with at least one radical polymerizable groups of average per molecule; The existence that wherein is aggregated in following component takes place down: component (C), at least a organo-borane radical initiator; Component (D) is with the immiscible at least a non-solvent of component (A); Component (E) randomly, at least a organonitrogen reactive compounds; Component (F) randomly is applicable at least a activeconstituents of personal care and health care products; Component (G) randomly, at least a emulsifying agent; And oxygen, keep simultaneously from about 5 ℃ to about 95 ℃ temperature.
30. personal care product according to claim 29 or health care products; But wherein said absorption fluids is selected from decamethylcyclopentaandoxane, Permethyl 99A., NSC 109495 or is selected from the mixture of ester class, Standamul G or the Standamul G of Salacos 913, PEG-4 two heptanoates, PIVALIC ACID CRUDE (25) isooctadecanol ester, PIVALIC ACID CRUDE (25) 13 esters, sad hexadecyl ester, cetyl palmitate, ricinolic acid hexadecyl ester, Triple Pressed Stearic Acid hexadecyl ester, tetradecanoic acid hexadecyl ester, two caprylic/capric cocoyl esters, Unimac 5680 ester in the last of the ten Heavenly stems, Isodecyl oleate, Isodecyl Neopentanoate, PIVALIC ACID CRUDE (25) dissident ester, Wickenol 155, oxysuccinic acid dioctyl ester, sad 13 esters, Tetradecyl tetradecanoate, Acetylated lanolin alcohols, cetyl acetate, Permethyl 99A. alcohol, polyglyceryl-3-diisopstearate, and composition thereof.
31. personal care product according to claim 29 or health care products, wherein component (A) is selected from the YSR 3286 and the resin of the functional YSR 3286 of methacrylic ester and resin and acrylate-functional.
32. personal care product according to claim 29 or health care products; Wherein component (B) is selected from TEB 3K, stearyl methacrylate, methylacrylic acid benzene methyl, methylacrylic acid tetrahydrofuran ester, methylacrylic acid 2-hydroxyl ethyl ester, dimethylaminoethyl methacrylate, N, N-DMAA, n-vinyl formamide, 4-vinylpridine, l-vinyl-2-pyrrolidone, vinylformic acid, methylacrylic acid and N-NSC 11448.
33. personal care product according to claim 29 or health care products, wherein component (C) is selected from boron triethyl-propanediamine mixture, boron triethyl-NSC 158165 mixture, boron triethyl-methoxy propyl amine compound and three normal-butyl methoxy propyl amine compounds.
34. personal care product according to claim 29 or health care products, wherein component (D) is selected from water, acetone, methyl alcohol, ethanol and its combination.
35. personal care product according to claim 29 or health care products, wherein optional components (E) is selected from acetate, vinylformic acid, Hydrocerol A and the end capped YSR 3286 of dimethyl-carboxy decyl.
36. personal care product according to claim 29 or health care products, wherein optional components (F) is selected from VITAMINs, opalizer, plant milk extract, spices or essence, part drug's actives, albumen, enzyme, antiperspirant, reodorant, moistening agent, anti-mycotic agent and antiseptic-germicide.
37. personal care product according to claim 29 or health care products, wherein optional components (G) is selected from Tergitol
TM15-s-3, Tergitol
TM15-s-40, poly ethyldiol modified trimethyl silicone hydride silicate, poly ethyldiol modified siloxanes, poly ethyldiol modified silicon-dioxide, ethoxylated quaternary solution and palmityl trimethyl ammonium chloride solution.
38., be selected from antiperspirant, reodorant, protective skin cream, skin-care liquid, moistening agent, facial-care article, facial cleansing article, bath oil, perfume, Gu Longshui, sachet, sunscreen, the preceding lotion that shaves, aftershave lotion, liquid soap, body wash, solid soap, shaving soap, shaving foam, shampoo, hair conditioner, hair dye, hair spray, mousse, agent for permanent hair waving, trichogen, stratum corneum maintenance element, makeup, color make-up, foundation cream, rouge, lipstick, lip oil, eyeliner, Mascara, eye shadow, makeup removing oil and color make-up makeup removing agent according to described personal care of claim 37 or health care products.
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US25448109P | 2009-10-23 | 2009-10-23 | |
US61/254,481 | 2009-10-23 | ||
PCT/US2010/053145 WO2011049919A1 (en) | 2009-10-23 | 2010-10-19 | Hydrophilically-modified silicone compositions |
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CN102666620A true CN102666620A (en) | 2012-09-12 |
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CN2010800586639A Pending CN102666620A (en) | 2009-10-23 | 2010-10-19 | Hydrophilically-modified silicone compositions |
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US (1) | US9624334B2 (en) |
EP (1) | EP2491065B1 (en) |
JP (1) | JP5738877B2 (en) |
KR (1) | KR20120101015A (en) |
CN (1) | CN102666620A (en) |
WO (1) | WO2011049919A1 (en) |
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CN103301041A (en) * | 2013-06-29 | 2013-09-18 | 上海艳紫化工科技有限公司 | Fibroin amino acid repair hair conditioner |
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Also Published As
Publication number | Publication date |
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US20120237464A1 (en) | 2012-09-20 |
JP5738877B2 (en) | 2015-06-24 |
EP2491065B1 (en) | 2014-11-26 |
US9624334B2 (en) | 2017-04-18 |
JP2013508510A (en) | 2013-03-07 |
WO2011049919A1 (en) | 2011-04-28 |
EP2491065A1 (en) | 2012-08-29 |
KR20120101015A (en) | 2012-09-12 |
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